US 6,168,655 AGrant

Colorant stabilizers

Issue Date:2001-01-02

•77 Claims

Abstract

The present invention is directed to an ink set of inks which have substantially identical light fastness properties. The ink set includes ink compositions containing a colorant and at least one colorant stabilizer. The colorant stabilizer imparts light-stability to the colorant so that the colorant does not fade when exposed to electromagnetic radiation such as sunlight or artificial light. The ink set provides a range of colored inks having similar light-stability.

Metadata

Assignee

Kimberly-Clark Worldwide, Inc.

Inventors

Ronald Sinclair Nohr
John Gavin MacDonald

Application Information

Application Number:US 09/211,895

Filing Date:1998-12-15

Priority Date:1995-11-28

Art Unit:7

Classifications

IPC:

C09D 1102

Field of Search:

106 3158106 3186106499

Patent Drawings

This patent does not have any drawings.

Description

[0002] This patent application is a divisional of U.S. patent application Ser. No. 08/843,410 filed on Apr. 15, 1997, now U.S. Pat. No. 5,855,655; which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/788,863 filed on Jan. 23, 1997; which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/757,222 filed on Nov. 27, 1996, now U.S. Pat. No. 5,782,963; which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/627,693 filed on Mar. 29, 1996, now abandoned; which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/589,321 filed on Jan. 22, 1996; which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/563,381 filed on Nov. 28, 1995, now abandoned; all of which are incorporated herein by reference.

Technical Field

[0003] The present invention relates to a family of colorant stabilizers. The colorant stabilizers, according to the present invention, are capable of stabilizing a colorant when it is exposed to electromagnetic radiation. The colorant stabilizers enable the production of an ink set wherein each ink of the ink set, regardless of color, possesses substantially similar light fastness properties.

Background of the Invention

[0004] A major problem with colorants is that they tend to fade when exposed to electromagnetic radiation such as sunlight or artificial light and the like. It is believed that most of the fading of colorants when exposed to light is due to photodegradation mechanisms. These degradation mechanisms include oxidation or reduction of the colorants depending upon the environmental conditions in which the colorant is placed. Fading of a colorant also depends upon the substrate upon which they reside.

[0005] Product analysis of stable photoproducts and intermediates has revealed several important modes of photodecomposition. These include electron ejection from the colorant, reaction with ground-state or excited singlet state oxygen, cleavage of the central carbon-phenyl ring bonds to form amino substituted benzophenones, such as triphenylmethane dyes, reduction to form the colorless leuco dyes and electron or hydrogen atom abstraction to form radical intermediates.

[0006] Various factors such as temperature, humidity, gaseous reactants, including O₂, O₃, SO₂, and NO₂, and water soluble, nonvolatile photodegradation products have been shown to influence fading of colorants. The factors that effect colorant fading appear to exhibit a certain amount of interdependence. It is due to this complex behavior that observations for the fading of a particular colorant on a particular substrate cannot be applied to colorants and substrates in general.

[0007] Under conditions of constant temperature it has been observed that an increase in the relative humidity of the atmosphere increases the fading of a colorant for a variety of colorant-substrate systems (e.g., McLaren, K., J. Soc. Dyers Colour,1956, 72, 527). For example, as the relative humidity of the atmosphere increases, a fiber may swell because the moisture content of the fiber increases. This aids diffusion of gaseous reactants through the substrate structure.

[0008] The ability of a light source to cause photochemical change in a colorant is also dependent upon the spectral distribution of the light source, in particular the proportion of radiation of wavelengths most effective in causing a change in the colorant and the quantum yield of colorant degradation as a function of wavelength. On the basis of photochemical principles, it would be expected that light of higher energy (short wavelengths) would be more effective at causing fading than light of lower energy (long wavelengths). Studies have revealed that this is not always the case. Over 100 colorants of different classes were studied and found that generally the most unstable were faded more efficiently by visible light while those of higher lightfastness were degraded mainly by ultraviolet light (McLaren, K., J. Soc. Dyers Colour,1956, 72, 86).

[0009] The influence of a substrate on colorant stability can be extremely important. Colorant fading may be retarded or promoted by some chemical group within the substrate. Such a group can be a ground-state species or an excited-state species. The porosity of the substrate is also an important factor in colorant stability. A high porosity can promote fading of a colorant by facilitating penetration of moisture and gaseous reactants into the substrate. A substrate may also act as a protective agent by screening the colorant from light of wavelengths capable of causing degradation.

[0010] The purity of the substrate is also an important consideration whenever the photochemistry of dyed technical polymers is considered. For example, technical-grade cotton, viscose rayon, polyethylene, polypropylene, and polyisoprene are known to contain carbonyl group impurities. These impurities absorb light of wavelengths greater than 300 nm, which are present in sunlight, and so, excitation of these impurities may lead to reactive species capable of causing colorant fading (van Beek, H. C. A., Col. Res. Appl.,1983, 8(3), 176).

[0011] Therefore, there exists a need for methods and compositions which are capable of stabilizing a wide variety of colorants from the effects of both sunlight and artificial light.

Summary of the Invention

[0012] The present invention addresses the needs described above by providing compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range.

[0013] The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a colorant stabilizer. In one embodiment, the colorant stabilizer of the present invention is an aryliminealkene having the following general formula:

[0014] wherein

[0015] R₁is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

[0016] R₂is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

[0017] R₃is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

[0018] R₄is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or substituted aryl group; and

[0019] R₅is an aryl, heteroaryl, polyalkene, or substituted aryl group;

[0020] wherein R₁, R₂, or R₄is an aryl, heteroaryl, or substituted aryl group.

[0021] Desirably, the alkene group is in the trans configuration.

[0022] In another embodiment of the present invention, heavy atoms are added to conventional dyes to stabilize the dyes. These heavy atoms include Group VII ions including iodide ions. It has further been determined that the counterion is desirably a large ion with a relatively low charge density. These counterions should be sodium or larger. The counterions also include relatively large organic counterions such as tetramethylammonium.

[0023] In yet another embodiment of the present invention, highly effective dye stabilizers include derivatives of phenols with the following general formula:

[0024] wherein

[0025] R₁is iodine, or an alkyl group having between 1 and 5 carbon atoms;

[0026] R₂is an iodine, or an alkyl group having between 1 and 5 carbon atoms;

[0027] R₃is iodine, or an alkyl group having between 1 and 5 carbon atoms; and

[0028] R₄is a sugar, polyhydroxy compound, sulfonic acid salt compound, carboxylic acid salt compound, polyether compound, or hydrogen, wherein the sugar includes, but is not limited to, glucose, fructose, polyether sugars, monosaccharides, polysaccharides, cyclodextrins, including but not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin. In particular, the triiodophenols and trimethylphenols and the water soluble derivatives thereof are particularly effective in stabilizing a wide variety of dyes.

[0029] In yet another embodiment, the colorant stabilizer of the present invention is a reducing agent. The reducing agent includes, but is not limited to, sodium thiosulfate (Na₂S₂O₃), sodium sulfite (Na₂SO₃), cysteine, sodium nitrite, sodium phosphite, and citric acid. A desired reducing agent is sodium thiosulfate. In this embodiment, the stabilizer may be admixed with the colorant, or it may be applied to a substrate to which the colorant will be applied. Although the reducing agent alone stabilizes a colorant, it is desirable that the reducing agent is combined with one or more of the above stabilizers.

[0030] In another embodiment, the colorant stabilizer of the present invention is a molecular includant having a chemical structure which defines at least one cavity. The molecular includant may be on or in a substrate to which the colorant will be applied, or it may be present in a colorant solution. The molecular includant may be, but is not limited to, clathrates, zeolites, crown ethers, calixarenes, valinomycin type natural antibiotics, various polyether compounds, nigericin type natural antibiotics, and cyclic compounds containing a plurality of pyranose rings. The cyclic compounds include, but are not limited to, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, and derivatives thereof. A desired molecular includant is cyclodextrin. A more desired molecular includant is γ-cyclodextrin. Desirably, the molecular includant is present on or in the substrate to which the colorant will be applied.

[0031] The substrates to which the colorant stabilizers are applied include, but are not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal, or any other substrate that would benefit from having a stabilized colorant thereon.

[0032] Although the molecular includant in or on the substrate stabilizes a colorant that is applied thereto, it is desirable that the colorant is combined with one or more of the above stabilizers. Additionally, in the embodiment where the molecular includant is present in a colorant solution, the colorant stabilizing molecules can be associated with one or more molecular includants. Additionally, the includants can have multiple colorant stabilizing molecules associated therewith. In some embodiments, the colorant is at least partially included within a cavity of the molecular includant and the colorant stabilizing molecules are associated with the molecular includant outside of the cavity. In some embodiments, the colorant stabilizing molecules are covalently coupled to the outside of the molecular includant.

[0033] In another embodiment, a colorant stabilizer, such as a molecular includant, is present in a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing.

[0034] In another embodiment, a colorant stabilizer comprise one or more porphines that have an extremely short triplet state lifetime. (See e.g., Kub{acute over (a)}t, et al., Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) porphyrin, J. Photochem. and Photbio. A: Chemistry96 (1996), pgs 93-97 which is incorporated herein by reference). Particularly suitable porphines include, but are not limited to, porphines having the following structure:

[0035] wherein R is any proton-donating moiety and M is cobalt or copper. Desirably, R is SO₃H,

[0036] COOH, or R₁COOH wherein R₁is an alkyl group of from 1 to 6 carbons.

[0037] Examples of such porphines are Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures:

[0038] wherein the copper ion can also be substituted with a cobalt ion. Other metal ions, such as an iron ion, can be substituted in the porphine molecule as long as the molecule has a relatively short-lived triplet state.

[0039] In a further embodiment, the colorant stabilizer comprises at least one metal or metal salt, alone or in combination with, at least one other colorant stabilizer of the present invention. Desirably, the metal or metal salt is used in combination with at least one other colorant stabilizer, such as a porphine or a benzophenone. Unexpectedly, it has been discovered that the incorporation of a relatively small concentration of metal or metal salt into a porphine-containing composition results in superior colorant stability. Preferred metals or metal salts include, but are not limited to, lanthanides and lanthanide salts. Lanthanide elements include scandium, yttium, lanthanum, cerium praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Other suitable metal and metal salts include magnesium, iron, zinc, other transition metals, and heavy metals.

[0040] In order to improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may be added. Particularly useful metal solubility-enhancing agents include, but are not limited to, chelating agents. Optionally, a surfactant can be added to the metal/porphine composition to increase the interaction of the metal or metal salt and the porphine. In addition to surfactants, other additives such as TINUVIN® compounds (Ciba-Geigy Corporation) may be incorporated into the colorant composition.

[0041] The colorant stabilizing additive can also optionally be dimethyl amino benzoic acid quat (designated DMABAQ), represented by the following structure:

[0042] The colorant stabilizing additive can also optionally be a basic fuschin hydrazone, represented by the following structure:

[0043] In addition, the colorant stabilizing additive of this invention is a benzophenone, of the general formula:

[0044] wherein R represents any substituents which permit the benzophenone to function as a colorant stabilizer.

[0045] Accordingly, each of these embodiments of the present invention provide stabilizing molecules that, when one or more of the stabilizing molecules are associated with a colorant, stabilizes the colorant. Therefore, the stabilizing molecules can be used as an additive to any colorant composition. For example, as certain of the stabilizing molecules are poorly soluble in water, they can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the stabilizing molecules can be added to other colorant compositions that contain additives enabling the solubilization of the stabilizing molecule therein. Further, the stabilizing molecules can be solubilized in an aqueous solution by attaching the molecule to a large water soluble molecule, such as a cyclodextrin.

[0046] The colorant stabilizers are particularly effective in ink jet inks. Use of the colorant stabilizers, as described herein, intensifies the colors and stabilizes the colors when exposed to light. Additionally, the colorant stabilizers are particularly effective in paper such as ink jet paper. Use of the colorant stabilizers in a substrate, as described herein, stabilizes a colorant to which it is applied. Also, colorant stabilizers in a substrate has been found to have the unexpected result of reducing the yellowing of the substrate itself upon exposure to light.

[0047] The colorant stabilizers are of particular interest in the formation of ink sets, wherein each ink of the ink set, regardless of color, possesses substantially identical light fastness properties as the other inks in the ink set. The ink set enables the production of multi-color text and/or graphics, which uniformly retain their color over extended periods of time and/or upon extended exposure to light.

[0048] These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

Detailed Description of the Invention

[0049] This application is directed to compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. This application is further directed to ink sets comprising four or more inks, each of which possesses substantially identical light stability upon exposure to radiation, including radiation in the visible wavelength range. The compositions and methods relating to stabilizing a colorant by admixing a stabilizing molecule with a colorant solution will first be addressed below. Subsequently, the compositions and methods relating to stabilizing a colorant by applying the colorant to a treated substrate containing a stabilizing molecule will be discussed.

[0050] Admixing Stabilizing Molecules into Colorant Solutions

[0051] The present invention relates to colorant compositions having improved stability, wherein the colorant stabilizer is associated with a colorant solution. Desirably, the colorant stabilizer is admixed with a colorant solution. The colorant stabilizer is desirably an aryliminealkene compound. Other desired colorant stabilizers are heavy atoms such as the iodide ion, phenol derivatives such as triiodophenol, trimethylphenol, and metals or metal salts, and derivatives thereof. Additional colorant stabilizers include reducing agents such as sodium thiosulfate. Furthermore, colorant stabilizers include porphines alone or in combination with at least one metal or metal salt; hydrazones; benzophenones; and combinations of one or more of the above colorant stabilizers. The colorant stabilizers of the present invention are admixed with a colorant to stabilize the colorant when the admixture is exposed to electromagnetic radiation such as artificial light or sunlight.

[0052] The present invention further relates to a method of stabilizing a colorant comprising associating one or more of the colorant stabilizers with the colorant solution. Optionally, the colorant stabilizer may be associated with a molecular includant, chelating agent, or other material to improve solubility and/or interaction of the colorant stabilizer and the colorant.

[0053] The present invention is particularly useful for stabilizing inks to be used in ink jet printers. Inks used in ink jet printers are described in U.S. patent application Ser. No. 08/769,885 filed on Dec. 19, 1996, which is a continuation of U.S. patent application Ser. No. 08/461,382 filed on Jun. 5, 1995, now abandoned, which is a divisional of U.S. patent application Ser. No. 08/461,365 filed on Jun. 5, 1995, now abandoned, all of which are incorporated herein by reference.

[0054] Thus, in one embodiment, the aryliminealkene stabilizing composition is shown by the following general formula:

[0055] wherein

[0056] R₁is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

[0057] R₂is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

[0058] R₃is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

[0059] R₄is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or substituted aryl group; and

[0060] R₅is an aryl, heteroaryl, or substituted aryl group;

[0061] wherein R₁, R₂, or R₄is an aryl, heteroaryl, or substituted aryl group.

[0062] Desirably, the alkene group is in the trans configuration.

[0063] Desirably, the aryliminealkene stabilizing compound has one of the following formulae:

[0064] Accordingly, this embodiment of the present invention provides a stabilizing molecule, the above aryliminealkene, which when associated with a colorant, stabilizes the colorant. Therefore, the above aryliminealkene can be used as an additive to any colorant composition. For example, as certain of the aryliminealkene compounds are poorly water soluble, they can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the aryliminealkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein. Further, the aryliminealkene stabilizing compounds can be solubilized in an aqueous solution by associating the compound with a large water soluble molecule, such as a cyclodextrin.

[0065] The term “composition” and such variations as “colored composition” are used herein to mean a colorant and one or more colorant stabilizers of the present invention. The composition can optionally include molecular includant.

[0066] As used herein, the term “colorant” is meant to include, without limitation, any material which typically will be an organic material, such as an organic colorant or dye. The term is meant to include a single material or a mixture of two or more materials.

[0067] The term “light-stable” is used herein to mean that the colorant, when associated with one of the colorant stabilizing molecules of the present invention, is more stable to electromagnetic radiation, including, but not limited to, sunlight or artificial light, than when the colorant is not associated with such a compound.

[0068] The term “molecular includant,” as used herein, is intended to mean any substance having a chemical structure which defines at least one cavity. That is, the molecular includant is a cavity-containing structure. As used herein, the term “cavity” is meant to include any opening or space of a size sufficient to accept at least a portion of the colorant.

[0069] The term “functionalized molecular includant” is used herein to mean a molecular includant to which one or more molecules of a colorant stabilizer are covalently coupled to each molecule of the molecular includant. The term “degree of substitution” is used herein to refer to the number of these molecules or leaving groups (defined below) which are covalently coupled to each molecule of the molecular includant.

[0070] The term “derivatized molecular includant” is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular includant. The term “leaving group” is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of molecular includants include, but are not limited to, the cyclodextrins.

[0071] The term “artificial light” is used herein to mean light having a relatively broad bandwidth that is produced from conventional light sources, including, but not limited to, conventional incandescent light bulbs and fluorescent light bulbs.

[0072] The term “thereon” is used herein to mean thereon or therein. For example, the present invention includes a substrate having a colored composition thereon. According to the definition of “thereon” the colored composition may be present on the substrate or it may be in the substrate.

[0073] In several embodiments, the colorant stabilizer may be optionally associated with a molecular includant. It is to be noted that in all the compositions that contain a molecular includant, the number of such stabilizer molecules can be between approximately 1 and approximately 21 molecules per molecular includant. Of course, in certain situations, there can be more than 21 molecules per molecular includant molecule. Desirably, there are more than three of such stabilizer molecules per molecular includant.

[0074] The degree of substitution of the functionalized molecular includant may be in a range of from 1 to approximately 21. As another example, the degree of substitution may be in a range of from 3 to about 10. As a further example, the degree of substitution may be in a range of from about 4 to about 9.

[0075] In some embodiments of the present invention, the colorant is associated with the molecular includant. The term “associated” in its broadest sense means that the colorant is at least in close proximity to the molecular includant. For example, the colorant may be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. Alternatively, the colorant may be covalently bonded to the molecular includant, although this normally is neither desired nor necessary. As a further example, the colorant may be at least partially included within the cavity of the molecular includant.

[0076] The dye or colorant, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-α-[4-(dimethylamino)phenyl]-α-phenyl-benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)phenyl]phenyl-methylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)- phenyl]-phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)-phenyl]phenylmethylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and β-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt]; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2-[(hydrazino- carbonyl)amino]-2,3-dihydro-1 ,3-dioxo-1H-benz[de]iso- quinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7-[[4-(dimethyl-amino)phenyl]azo]-5-phenylphenazinium chloride}; cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2-[7-[1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H- benz[e]indol-2-ylidene]-1,3,5-heptatrienyl]-1,1-dimethyl-3-(4- sulfobutyl)-1H-benz[e]indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H- indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methyl-coumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 [bisbenzimide or 2-(4-hydroxyphenyl)-5-(4- methyl-1-piperazinyl)-2,5-bi-1H-benzimidazole trihydrochloride pentahydrate]; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,11b-dihydrobenz[b]- indeno[1,2-d]pyran-3,4,6a,9,10(6H)-pentol}; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxybenzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 [N-(2,4-dinitrophenyl)-1,4-phenylenediamine or Solvent Orange 53]; diazo dyes, such as Disperse Orange 13 [Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene]; anthraquinone dyes, such as Disperse Blue 3 [Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone], Disperse Blue 14 [Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone], and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3-[(4-[(4-[(6-amino-1- hydroxy-3-sulfo-2-naphthalenyl)azo]-6-sulfo-1-naphthalenyl)- azo]-1 -naphthalenyl)azo]-1,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2,7-dichlorofluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)-[29H,31H- phthalocyanato(2-)-N²⁹,N³⁰,N³¹,N³²]copper}; carotenoid dyes, such as trans-B-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9,10-dihydro- 3,5,6, 8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracene- carbonylic acid); azure dyes, such as Azure A [3-amino-7- (dimethylamino)phenothiazin-5-ium chloride or 7-(dimethyl- amino)-3-imino-3H-phenothiazine hydrochloride]; and acridine dyes, such as Acridine Orange [Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt] and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridine-diamine).

[0077] In preparing the aryliminealkene colorant stabilizer of the present invention, one can, for example, start with a chalcone which is represented by the following formula:

[0078] It is to be understood that the phenyl groups on the chalcone can be substituted with a wide variety of substituents. The chalcone is then reacted with a primary amine having the following general formula:

[0079] NH₂—R

[0080] wherein R is an aryl, heteroaryl, or substituted aryl group. A desirable primary amine is 2 amino benzene sulfonic acid. The reaction is carried out in a nonaqueous solvent such as absolute alcohol. The resulting compound has the following general structure:

[0081] Accordingly, one colorant stabilizer of the present invention is an aryliminealkene having the following general formula:

[0082] wherein if R₁is an aryl group, then R₂is a hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and if R₂is an aryl group, then R₁is hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group. R₃is an aryl, heteroaryl, or substituted aryl group. Desirably, the alkene group is in the trans configuration.

[0083] Desirably, the aryliminealkene stabilizing compound has one of the following formulae:

[0084] The SO₃H group can be in the ortho, meta or para position.

[0085] Yet another aryliminealkene compound is an imine adduct of basic fuschin and is shown in the following formula:

[0086] The imine adduct of basic fuschin can be synthesized according to Example 7 below.

[0087] In the embodiment where the aryliminealkene compound is covalently attached to another molecule, whichever R₁or R₂that is an aryl group will have a group including, but not limited to, a carboxylic acid group, an aldehyde group, an amino group, a haloalkyl group, a hydroxyl group, or a thioalkyl group attached thereto to allow the aryliminealkene to be covalently bonded to the other molecule. Accordingly, the aryliminealkene stabilizing compound is represented by one of the following formulae:

[0088] wherein R is an aryl, heteroaryl, or substituted aryl group. Although it is preferred that the group attached to the aryl group is para to the remainder of the stabilizer molecule, the group may also be ortho or meta to the remainder of the molecule.

[0089] Accordingly, this embodiment of the present invention provides a stabilizing aryliminealkene which, when associated with a colorant, stabilizes the colorant. Therefore, the above aryliminealkenes can be used as an additive to any colorant composition. For example, if the aryliminealkene compound is not water soluble or is poorly water soluble, it can be directly added to solvent or oil colorant compositions. Additionally, the aryliminealkene compound can be added to other colorant compositions that contain additives enabling the solubilization of the compound therein.

[0090] This embodiment provides a method for stabilizing a colorant by admixing the aryliminealkene compound with the colorants in an amount effective to stabilize the colorant. The aryliminealkene desirably should be present in the colorant solution at a concentration of approximately 0.1 to 50% by weight, desirably between approximately 20% and 30% by weight. In other words, the aryliminealkene should be equivalent in concentration to the colorant or should be at a higher concentration than the colorant. If no cyclodextrin or derivatized cyclodextrin is used, the desirable range is approximately 1 part dye to approximately 20 parts aryliminealkene.

[0091] Although the aryliminealkene compound need only be associated with the colorant, in some embodiments of the present invention, the aryliminealkene compound may be covalently bonded to the colorant.

[0092] Another embodiment of the present invention is amino sulfonic acid represented by the following formula:

[0093] The SO₃H group can be in the ortho, meta or para position.

[0094] Another embodiment of colorant stabilizers include derivatives of phenols with the following general formula:

[0095] wherein

[0096] R₁is iodine, or an alkyl group having between 1 and 5 carbon atoms;

[0097] R₂is an iodine, or an alkyl group having between 1 and 5 carbon atoms;

[0098] R₃is iodine, or an alkyl group having between 1 and 5 carbon atoms; and

[0099] R₄is a sugar, polyhydroxy compound, sulfonic acid salt compound, carboxylic acid salt compound, polyether compound, or hydrogen, wherein the sugar includes, but is not limited to, glucose, fructose, polyether sugars, monosaccharides, polysaccharides, cyclodextrins, including but not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin.

[0100] The phenol derivatives are desirably added to the colorant solution at a concentration of between 0.5 and 10 molar equivalents to the concentration of the colorant.

[0101] A desired colorant stabilizer is triodophenol (Aldrich). The triiodophenol has the following formula:

[0102] The triiodophenolates are desirably added to the colorant solution at a concentration of between 0.5 and 10 equivalents to the concentration of the colorant.

[0103] A desired colorant stabilizer includes trimethylphenol and derivatives thereof. The trimethylphenols have the following formula, wherein one or more of the methyl groups may be substituted with another alkyl or alkenyl group:

[0104] The trimethylphenols are desirably added to the colorant solution at a concentration of between 0.5 and 10 equivalents to the concentration of the colorant. Similarly, another desired colorant stabilizer is triiodophenol, which is desirably added to the colorant solution at a concentration of between 0.5 and 10 equivalents to the concentration of the colorant.

[0105] Further, the water solubility of the stabilizing compounds, including but not limited to the aryliminealkenes or triiodophenols or the trimethyphenols, can be increased by a variety of means. The desirable means of increasing the water solubility of the phenol-based stabilizing compounds is to add a water soluble moiety to the hydroxyl group on the phenol. In this embodiment, R₄of the above phenol figure is a sugar, polyhydroxy compound, sulfonic acid salt compound, carboxylic acid salt compound, or polyether compound, wherein the sugar includes, but is not limited to, glucose, fructose, polyether sugars, monosaccharides, polysaccharides, cyclodextrins, including but not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin.

[0106] Accordingly, in one embodiment of the present invention the means of increasing the water solubility of the stabilizing compounds of the present invention is to react the phenol with a sugar, to produce the following representative compounds:

[0107] wherein R is any group capable of rendering the phenol more water soluble. More particularly, the R group may be, but is not limited to a sugar, polyhydroxy compound, sulfonic acid salt compound, carboxylic acid salt compound, or polyether compound, wherein the sugar includes, but is not limited to, glucose, fructose, polyether sugars, monosaccharides, polysaccharides, cyclodextrins, including but not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin. A desired R group is 1,2-o-isopropylidene-D-glucofuranose. The resultant desired stabilization compound is represented by one of the following formulae:

[0108] Examples 21, 22 and 24 describe how to prepare the above water soluble phenols. A more desired R group is glucose, where the ketal group of the above phenol-sugar compounds has been removed as described in Examples 23 and producing the stabilizing compounds shown below:

[0109] The colorant stabilizer compounds above in which the ketal group has been removed is a more desired stabilizer compound as it is more water soluble than if the ketal group is present.

[0110] Another desired colorant stabilizing compound is 3-(2,4,6-triiodophenoxy)-1,2-propanediol, as shown below:

[0111] Another means of increasing the water solubility of the stabilizing compounds of the present invention is to associate the compound to a large water soluble molecule, such as a cyclodextrin or desirably a derivatized cyclodextrin. Desirably, the derivatized cyclodextrin is ethylhydroxy β-cyclodextrin. An example of such a covalent association of the stabilizing compounds is the triiodophenol or the trimethylphenol covalently bound with an ethylhydroxy β-cyclodextrin as represented in the following formulae:

[0112] wherein n=1 to 21 and CD=cyclodextrin. The aryliminealkenes can be covalently attached to the β-cyclodextrin via any suitable functional group. An example of such an association is represented in the following formula:

[0113] wherein R is an aryl, heteroaryl, or substituted aryl group, n=1 to 21 and CD=β-cyclodextrin. It is to be understood that any of the aryliminealkenes can be covalently attached to the derivatized cyclodextrin through the appropriate functional groups. The water solubility of the triiodophenols or the trimethyphenols can be increased by adding a soluble compound to the molecule.

[0114] The association can be an admixture or can be a covalent attachment. Desirably, between about 1 and 12 stabilizing molecules can be attached to a cyclodextrin molecule. More desirably, between about 4 to about 9 stabilizing molecules are attached to a cyclodextrin molecule. Accordingly, the stabilizing compound attached to cyclodextrin can be added to any aqueous colorant system to stabilize the colorant therein. It is to be understood that the stabilizing aryliminealkenes do not have to be attached to the molecular includants to exhibit their stabilizing activity.

[0115] Although not wanting to be limited by the following, it is thought that the stabilizer compounds of the present invention exhibit excellent stabilizing properties as their high water solubility maintains the amount of additive present in solution over time, so that the additive continues to provide its stabilization properties to the admixture. A stabilizing additive precipitating out of a colorant composition negatively impacts the composition as less of the stabilizer remains in the solution, and therefore the colorant composition is less stabilized. Further, if the stabilizing additive is used in ink jet inks and cartridges, such precipitation can clog the ink jet printer and can other wise negatively impact the printing quality of the ink. A surprising and unexpected feature of the present invention is that the stabilizing compound is extremely water soluble, and does not precipitate out of ink solutions over time.

[0116] A third class of colorant stabilizers that are considered part of the present invention are heavy atoms such as iodide, xenon, and lanthanides. These compounds are desirably associated with large counterions such as sodium or larger counterions such as nitrates. It has been determined that smaller counterions, such as potassium, provide poor stabilization of the colorants. The desirable salt is sodium iodide. Another desirable salt is tetramethyl ammonium iodide. A further desirable salt is europium nitrate. The preferred concentration of the heavy atoms is between approximately 0.5 to 5 mole equivalents. The heavy atom salt is added to the colorant before exposure to the electromagnetic radiation.

[0117] Examples 26 and 27 report the fade testing results of Hewlett Packard magenta ink admixed with various combinations of stabilizing compounds of the present invention. More particularly, 3 molar equivalents of the trimethylphenol sugar produced in Example 23, 4 molar equivalents of the triiodophenol sugar produced in Example 25, and two molar equivalents of sodium iodide were admixed with HP magenta ink having already admixed therein 2% by weight β-hydroxyethyl cyclodextrin. It is to be understood that the molar equivalents of the various stabilizing compounds can be varied. In comparison with the ink on the control sheets of paper and transparencies, the above described ink on paper and transparencies was much more stable. (See the tables in Example 26, and Example 27).

[0118] It is desirable that a colorant solution be stabilized with one or more of the following components in the following amounts: 2 to 10% wt/wt cyclodextrin or derivative thereof; 4-6% wt/wt of an aryliminealkene stabilizer of the present invention; 0.25 to 2 molar equivalents (eq) of an iodide; 2 to 7 eq of a triiodophenol sugar; 2 to 7 eq of a trialkyl phenol sugar; and 2 to 3 eq of ascorbic acid. More desirably, the colorant solution is to be stabilized with 2 to 10% wt/wt hydroxyethyl cyclodextrin; 4-6% wt/wt of an aryliminealkene stabilizer of the present invention; 0.25 to 2 molar equivalents (eq) of sodium iodide or tetramethyl amine iodide; 2 to 7 eq of a triiodophenol sugar; 2 to 7 eq of a trimethyl phenol sugar; and 2 to 3 eq of ascorbic acid. It is to be understood that units of “eq” or “molar equivalents” for stabilizing additives refers to molar equivalents of the stabilizing additives with respect to the dye. Additionally, it is to be understood that units of “wt/wt” for stabilizing additives refers to the weight of the additive with respect to the weight of the ink or colorant solution.

[0119] In another embodiment, a colorant solution is stabilized with the following: 4-10% fuschin imine adduct (Example 7); 0.25 to 2 eq of an iodide ion; and 2-10% β-cyclodextrin, desirably hydroxyethyl β-cyclodextrin.

[0120] In another embodiment described in Example 37, a colorant stabilizer, such as a molecular includant, is present in a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing.

[0121] In another embodiment of the present invention, a colorant stabilizer is represented by porphines having an extremely short triplet state lifetime. (See e.g., Kub{acute over (a)}t, et al., Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) porphyrin, J. Photochem. and Photbio. A: Chemistry96 (1996), pgs 93-97 which is incorporated herein by reference). Particularly suitable porphines include, but are not limited to, porphines having the following structure:

[0122] wherein R is any proton-donating moiety and M is cobalt or copper. Desirably, R is SO₃H,

[0123] COOH, or R₁COOH wherein R₁is an alkyl group of from 1 to 6 carbons.

[0124] Desirably, the colorant stabilizer is represented by the porphines Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine (designated CuTMPS4), having the following structure:

[0125] wherein the copper ion can also be substituted with a cobalt ion. It is also understood that in the case of CuTPPS4 or CoTPPS4, the sulfuric acid moieties may be substituted with salts when in solution, such as sodium salts. The colorant solution may be stabilized with about 0.1% to 10% wt/wt porphine, more preferably about 0.3% to 1% wt/wt porphine, and more preferably about 0.5% wt/wt porphine.

[0126] The above porphines are used as colorant stabilizers in colorant compositions described in Example 38. In another embodiment described in Example 38, the colorant stabilizing additive can also optionally be dimethyl amino benzoic acid quat (designated DMABAQ), represented by the following structure:

[0127] The colorant solution may be stabilized with about 0.1% to 15% wt/wt DMABAQ, more preferably about 0.5% to 10% wt/wt DMABAQ, and more preferably about 1% to 5% wt/wt DMABAQ.

[0128] In another embodiment, the colorant stabilizer comprises a metal or metal salt, such as magnesium and magnesium salt, alone or in combination with, other colorant stabilizers. Desirably, the amount of metal or metal salt in the colorant solution is from about 0.01% to 10% wt/wt metal, more desirably about 0.03% to 1% wt/wt metal, and more desirably about 0.05% wt/wt metal. Although lanthanides and lanthanide salts are desired metals, other metals, may also be used such as magnesium, iron, zinc, and other transition metals. To improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may be added. Particularly useful metal solubility-enhancing agents include, but are not limited to, chelating agents, including, but not limited to, EDTA (ethylenediaminetetraacetic acid) or EGTA (ethylene glycol-bis(β-aminoethyl ether)).

[0129] In a further embodiment, the colorant stabilizer comprises a porphine and a lanthanide, such as europium. Desirably, the amount of porphine in the colorant solution is from about 0.1% to 10% wt/wt porphine, more desirably about 0.3% to 1% wt/wt porphine, and more desirably about 0.5% wt/wt porphine. Desirably, the amount of lanthanide in the colorant solution is from about 0.01% to 10% wt/wt lanthanide, more desirably about 0.03% to 1% wt/wt lanthanide, and more desirably about 0.05% wt/wt lanthanide. Although europium and europium salts are desired lanthanides, other lanthanides, may also be used.

[0130] In another embodiment described in Example 40, the colorant stabilizing additive can also optionally be a basic fuschin hydrazone, represented by the following structure:

[0131] The colorant solution may be stabilized with about 0.1% to 15% wt/wt hydrazone, more preferably about 0.5% to 10% wt/wt hydrazone, and more preferably about 1% to 5% wt/wt hydrazone.

[0132] In addition, another embodiment of the colorant stabilizing additive of this invention as described in Example 41, is a benzophenone, of the general formula:

[0133] wherein R represents any substituents which permit the benzophenone to function as a colorant stabilizer. Suitable substituents include substituents which improve the solubility of the benzophenone in aqueous solutions and/or provide a high electron density next to the aromatic ring of the benzophenone. Suitable substituents include, but are not limited to, hydroxyl groups, alkyl ether groups, aryl ether groups, sulfonic acid groups and sodium carboxylate groups. The colorant solution may be stabilized with about 0.01% to 15% wt/wt benzophenone, more preferably about 0.3% to 5% wt/wt benzophenone, and more preferably about 0.5% to 1% wt/wt benzophenone.

[0134] Although not wanting to be limited by the following, it is theorized that the above stabilizing compounds of the present invention, either admixed with a colorant solution or on or in a substrate to which the colorant is applied, act by quenching the excited state of a dye molecule by efficiently retuning it to a ground state. This reduces the likelihood of an oxidative or other chemical reaction occurring which would render the dye chromophore colorless.

[0135] The quenching process can occur by a number of processes. One such process is referred to as the heavy atom effect (internal or external) in which atoms with a high atomic number, such as iodine, xenon and lanthanides, can effect the excited electronic transitions of the dye molecule by allowing here to fore forbidden electronic transitions to occur and by decreasing the excited state lifetimes. This effect permits the rapid return of the dye to its ground state.

[0136] Another quenching process involves back electron transfer. In this case, quenching of the excited dye molecule occurs through sequential electron transfer. The additive or quencher, and dye form an ion pair through electron donation within which back electron transfer leads to an overall deactivation of the excited energy donor, i.e., the dye.

[0137] Another quenching process involves a condition in which the quencher (additive) molecule has an excited energy state lower than the excited dye. In this case, it may be possible to transfer the excited energy to the quencher thereby allowing the dye molecule to return to its ground state. These mechanisms are more fully discussed in Chemistry and Light,Suppan, P., Published by The Royal Society of Chemistry, 1994, pgs 65-69 which is incorporated herein by reference.

[0138] In all cases, it is optionally desirable to add a molecular includant to the colorant solution. The molecular includant can be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin (American Maize-Products Company, Hammond, Ind.).

[0139] The term “derivatized cyclodextrin” as used herein means a cyclodextrin having more than two leaving groups covalently coupled to each molecule of cyclodextrin. The term “leaving group” is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of derivatized cyclodextrin includes, but is not limited to, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β and γ-cyclodextrin. A desired derivatized cyclodextrin is ethylhydroxy β-cyclodextrin.

[0140] A desired molecular includant is γ-cyclodextrin. Another desirable molecular includant is β-cyclodextrin. In other embodiments, the molecular includant is an ethyl hydroxy β-cyclodextrin. Although not wanting to be bound by the following theory, it is believed that the molecular includant inhibits the aggregation of the colorant molecule in solution. Other aggregation inhibitors that can be used in practicing the present invention are starches, pectins, amyloses, clathrates and the crown ethers. It is to be understood that the addition of derivatized cyclodextrins to an ink formulation for the purpose of inhibiting aggregation and/or stabilizing the dyes in the inks is considered one aspect of the present invention.

[0141] In some embodiments, the colorant and the colorant stabilizers are associated with the molecular includant. The term “associated”, in its broadest sense, means that the colorant and/or the colorant stabilizers are at least in close proximity to the molecular includant. For example, the colorant and/or the colorant stabilizers can be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, ionic bonding, hydrogen bonding, dipole-dipole interactions or the like.

[0142] Alternatively, either or both of the colorant and the colorant stabilizers can be covalently bonded to the molecular includant. In certain embodiments, the colorant will be associated with the molecular includant by means of hydrogen bonding and/or van der Waals forces or the like, while the stabilizing molecule is covalently bonded to the molecular includant. In other embodiments, the colorant is at least partially included within the cavity of the molecular includant, and the colorant stabilizer is located outside of the cavity of the molecular includant.

[0143] As a practical matter, the colorant, the colorant stabilizer and molecular includant are likely to be solids depending upon the constituents used to prepare the molecules. However, any or all of such materials can be a liquid. The colored composition can be a liquid either because one or more of its components is a liquid, or, when the molecular includant is organic in nature, a solvent is employed. Suitable solvents include, but are not limited to, amides, such as N,N-dimethylformamide; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone, methyl ethyl ketone, and methyl butyl ketone; aliphatic and aromatic hydrocarbons, such as hexane, octane, benzene, toluene, and the xylenes; esters, such as ethyl acetate; water; and the like. When the molecular includant is a cyclodextrin, particularly suitable solvents are the amides and sulfoxides.

[0144] In an embodiment where the composition of the present invention is a solid, the effectiveness of the above compounds on the colorant is improved when the colorant and the selected compounds are in intimate contact or in an association that approaches van der Waals radii. To this end, the thorough blending of the components, along with other components which may be present, is desirable. Such blending generally is accomplished by any of the means known to those having ordinary skill in the art. When the colored composition includes a polymer, blending is facilitated if the colorant and the colorant stabilizer are at least partly soluble in softened or molten polymer. In such case, the composition is readily prepared in, for example, a two-roll mill. Alternatively, the composition of the present invention can be a liquid because one or more of its components is a liquid.

[0145] For some applications, the composition of the present invention typically will be utilized in particulate form. In other applications, the particles of the composition should be very small. Methods of forming such particles are well known to those having ordinary skill in the art.

[0146] The colored composition optionally may also contain a carrier, the nature of which is well known to those having ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common.

[0147] Examples of thermoplastic polymers include, but are not limited to: end-capped polyacetals, such as poly(oxymethylene) or polyformaldehyde, poly(trichloroacetaldehyde), poly(n-valeraldehyde), poly(acetaldehyde), poly(propionaldehyde), and the like; acrylic polymers, such as polyacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(ethyl acrylate), poly(methyl methacrylate), and the like; fluorocarbon polymers, such as poly(tetrafluoroethylene), perfluorinated ethylenepropylene copolymers, ethylenetetrafluoroethylene copolymers, poly-(chlorotrifluoroethylene), ethylene-chlorotrifluoroethylene copolymers, poly(vinylidene fluoride), poly(vinyl fluoride), and the like; epoxy resins, such as the condensation products of epichlorohydrin and bisphenol A; polyamides, such as poly(6-aminocaproic acid) or poly(e-caprolactam), poly(hexamethylene adipamide), poly(hexamethylene sebacamide), poly(11-aminoundecanoic acid), and the like; polyaramides, such as poly(imino-1,3-phenyleneiminoisophthaloyl) or poly(m- phenylene isophthalamide), and the like; parylenes, such as poly-p-xylylene, poly(chloro-p-xylene), and the like; polyaryl ethers, such as poly(oxy-2,6-dimethyl-1,4-phenylene) or poly(p-phenylene oxide), and the like; polyaryl sulfones, such as poly(oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4- phenylene-isopropylidene-1,4-phenylene), poly(sulfonyl-1,4- phenyleneoxy-1,4-phenylenesulfonyl-4,4-biphenylene), and the like; polycarbonates, such as poly(bisphenol A) or poly(carbonyldioxy- 1,4-phenyleneisopropylidene- 1,4-phenylene), and the like; polyesters, such as poly(ethylene terephthalate), poly(tetramethylene terephthalate), poly(cyclohexylene-1,4-dimethylene terephthalate) or poly(oxymethylene-1,4-cyclohexylenemethyleneoxyterephthaloyl), and the like; polyaryl sulfides, such as poly(p-phenylene sulfide) or poly(thio-1,4-phenylene), and the like; polyimides, such as poly(pyromellitimido-1,4-phenylene), and the like; polyolefins, such as polyethylene, polypropylene, poly(1-butene), poly(2-butene), poly(1-pentene), poly(2-pentene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), 1,2-poly-1,3-butadiene, 1,4-poly- 1,3-butadiene, polyisoprene, polychloroprene, polyacrylonitrile, poly(vinyl acetate), poly(vinylidene chloride), polystyrene, and the like; and copolymers of the foregoing, such as acrylonitrile-butadienestyrene (ABS) copolymers, styrene-n-butylmethacrylate copolymers, ethylene-vinyl acetate copolymers, and the like.

[0148] Some of the more commonly used thermoplastic polymers include styrene-n-butyl methacrylate copolymers, polystyrene, styrene-n-butyl acrylate copolymers, styrene-butadiene copolymers, polycarbonates, poly(methyl methacrylate), poly(vinylidene fluoride), polyamides (nylon-12), polyethylene, polypropylene, ethylene-vinyl acetate copolymers, and epoxy resins.

[0149] Examples of thermosetting polymers include, but are not limited to, alkyd resins, such as phthalic anhydride-glycerol resins, maleic acid-glycerol resins, adipic acid-glycerol resins, and phthalic anhydride-pentaerythritol resins; allylic resins, in which such monomers as diallyl phthalate, diallyl isophthalate diallyl maleate, and diallyl chlorendate serve as nonvolatile cross-linking agents in polyester compounds; amino resins, such as aniline-formaldehyde resins, ethylene urea-formaldehyde resins, dicyandiamide-formaldehyde resins, melamine-formaldehyde resins, sulfonamide-formaldehyde resins, and urea-formaldehyde resins; epoxy resins, such as cross-linked epichlorohydrin-bisphenol A resins; phenolic resins, such as phenol-formaldehyde resins, including Novolacs and resols; and thermosetting polyesters, silicones, and urethanes.

[0150] In addition to the colorant, colorant stabilizer, and optional molecular includant, the colored composition of the present invention also can contain additional components, depending upon the application for which it is intended. Examples of such additional components include, but are not limited to, charge carriers; stabilizers against thermal oxidation; viscoelastic properties modifiers; cross-linking agents; plasticizers; charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinylstearate, and polyethylene powders; fillers such as calcium carbonate, clay and talc; surfactants; chelating agents; and TINUVIN® compounds; among other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. Desirable surfactants include , but are not limited to, C₁₂to C₁₈surfactants such as cetyl trimethyl ammonium chloride and carboxymethylamylose. TINUVIN® compounds are a class of compounds produced by Ciba-Geigy Corporation, which includes benzophenones, benzotriazoles and hindered amines. Desirable TINUVIN® compounds include, but are not limited to, 2-(2′-hydroxy-3-sec-butyl-5′-tert-butylphenyl)-benzotriazole, poly-(N-β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate and 2-(2′-hydroxy-3′,5′-ditert butylphenyl)-5-chloro-benzotriazole. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art.

[0151] When the colorant stabilizers of the present invention are used to stabilize the dyes in ink jet inks, it is desirable to filter the compositions through a small pore filter (0.45 μ) such as a Millipore® filter before the ink formulation is placed in an ink jet cartridge. This will reduce or eliminate clogging of the cartridge ink nozzles due to particulate matter.

[0152] The colorant stabilizers of the present invention enable the formation of ink sets, wherein each ink of the ink set, regardless of color, possesses similar light fastness properties as the other inks in the ink set. Such ink sets may be used to produce multi-color text and/or graphics, which uniformly retain their color over extended periods of time and/or upon extended exposure to light. One desirable ink set includes cyan, magenta, yellow and black inks, wherein the magenta ink contains colorant stabilizers in the form of a porphine and a metal, such as europium, and the yellow ink contains a colorant stabilizer in the form of a porphine without the metal. Another desirable ink set includes cyan, magenta, yellow and black inks, wherein the cyan ink contains a colorant stabilizer in the form of a benzophenone, and the magenta and yellow inks contain colorant stabilizers in the form of a porphine and a metal, such as europium.

[0153] It is to be understood that in any desired ink set, a single ink may be stabilized according to the present invention or several of the inks may be stabilized utilizing one or more of the stabilizing agents described herein. Other ink sets are within the scope of the present invention. Included in the present invention are ink sets wherein the black color is a pigment and the other colors in the ink set are dyes. Although ink sets wherein the inks possess substantially identical light fastness properties are desirable, in some embodiments, it may be desirable to produce ink sets wherein the inks within the ink set have specifically controlled, varying light fastness properties.

[0154] Treated Substrates

[0155] As stated above, colorant stabilizers may be present in a colorant solution, or present on or in a substrate to which the colorant is to be applied. When a colorant stabilizer is present in or on a substrate, the substrate is referred to as a “treated substrate”. In one embodiment of the present invention, a treated substrate contains a reducing agent thereon or therein. In another embodiment, a treated substrate contains a molecular includant thereon or therein. In yet another embodiment, a treated substrate contains a molecular includant and a reducing agent thereon or therein. The term “stabilizing agent” is used to denote the colorant stabilizer in or on a substrate.

[0156] The substrate may be, but is not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, or any other substrate that would benefit from having a stabilized colorant thereon. A plastic substrate includes, but is not limited to, a plastic film, a plastic nonwoven web, or a plastic woven web. A preferred substrate is paper. Any existing or future type of paper or paper products may be used in the present invention.

[0157] Examples of paper or paper products include, but not limited to, printing and writing papers, packaging and industrial papers, paperboard, and tissue papers. Examples of printing and writing papers include, but are not limited to the following: wood-free coated papers; wood-containing coated papers; wood-free uncoated papers such as bond and writing paper, envelopes, offset and opaque circular, carbonless, tablet, forms bond, ledger, mimeograph, and manifold, duplication, fax base, thermal base, technical papers, supercalandered, and specialty papers; uncoated wood-containing papers such as supercalandered, directory, specialty converting and publishing; bristols such as coated bristols, uncoated bleached bristols, tag, coated tag papers, file folders, and tabulating; and thin papers such as cigarette paper, bible paper, lightweight paper, lightweight specialty, manifold, cotton fiber papers, and specialty thin papers.

[0158] Examples of Packaging and industrial papers include, but are not limited to the following: breached Kraft paper such as grocers bags, shipping sacks, wrapping paper, and converting paper; unbleached Kraft paper such as grocers bags, shipping sacks converting paper, wrapping paper, and envelopes. Examples of paperboard include, but are not limited to the following: containerboard such as unbleached linerboard, bleached linerboard, corrugated medium, and chip and filler board; folding boxboard/folding cartonboard such as solid bleached sulfite, bleached and unbleached bristols, coated recycled board, coated unbleached Kraft, milk, cup, plate and foodservice stock (coated or uncoated), and folding board; gypsum wallboard; and tube/can and drum paperboard. Examples of tissue papers include, but are not limited to, sanitary tissues such as bathroom tissue, facial tissue, napkins, toweling, wiper stock, and other sanitary tissue papers.

[0159] Molecular Includant

[0160] As stated above, a molecular includant is defined as any substance having a chemical structure which defines at least one cavity, wherein a cavity includes any opening or space of a size sufficient to accept at least a portion of a compound, such as, but not limited to, a colorant. The molecular includant can be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Molecular includants include, but are not limited to, clathrates or intercalates, zeolites, crown ethers, calixarenes, valinomycin type natural antibiotics, various polyether compounds, nigericin type natural antibiotics, or cyclic compounds containing a plurality of pyranose rings, for example, those having formed cyclic compounds through 1,4 and 1,6 bonding of monosaccharides such as glucose, fructose, galactose, and the like, and disaccharides such as saccharose, maltose, lactose, and the like.

[0161] The cyclic compounds also include cyclodextrins such as alpha-cyclodextrin (or α-cyclodextrin), beta-cyclodextrin (or β-cyclodextrin), gamma-cyclodextrin (or γ-cyclodextrin), delta-cyclodextrin (or δ-cyclodextrin), and derivatives thereof such as hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α-cyclodextrin, carboxymethyl α-cyclodextrin, carboxymethyl β-cyclodextrin, carboxymethyl γ-cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β-cyclodextrin, octyl succinated γ-cyclodextrin, sulfated β-cyclodextrin and sulfated γ-cyclodextrin, hydroxyethyl γ-cyclodextrin, hydroxyisopropyl γ-cyclodextrin, hydroxypropyl γ-cyclodextrin, octyl succinate γ-cyclodextrin, and carboxymethyl γ-cyclodextrin.

[0162] The α-cyclodextrins contain 6 glucopyranose rings, the β-cyclodextrins contain 7 glucopyranose rings, the γ-cyclodextrins contain 8 glucopyranose rings, and the δ-cyclodextrins contain 9 glucopyranose rings. Cyclodextrins with 10, 11, or 12 glucopyranose rings may also be used in the present invention. A desirable cyclodextrin is any γ-cyclodextrin that is water soluble. In particular, hydroxyethyl γ-cyclodextrin, hydroxyisopropyl γ-cyclodextrin, and hydroxypropyl γ-cyclodextrin are desirable molecular includants for the present invention. Another desirable cyclodextrin is any β-cyclodextrin that is water soluble. In particular, hydroxyethyl β-cyclodextrin is a preferred cyclodextrin.

[0163] The cyclodextrins suitable for the inks of the present invention can also, if desired, be modified by the addition of substituents. Substituents generally replace either the entire hydroxyl group or the hydrogen atom on one or more of the hydroxyl groups of the cyclodextrin ring. Examples of substituents include acyl groups, wherein one or more of the hydroxyl groups is replaced with groups such as —OAc, —OC(O)CH₂CH₃, —OC(O)(CH₂)₂CH₃, —OC(O)(CH₂)₃CH₃, —OC(O)CF₃, —OC(O)Ph, or the like; alkyl and aryl groups, wherein one or more of the hydroxyl groups is replaced with groups such as —OCH₃, —OCH₂CH₃, —O(CH₂)₂CH₃, —OC (CH₃)₃, —OPh, or the like; tosyl (4-methylbenzenesulfonyl), or Ts or related groups, wherein one or more of the hydroxyl groups is replaced with —OTs or the like; mesyl (methanesulfonyl, or Ms) or related groups, wherein one or more of the hydroxyl groups is replaced with —OMs or the like; amino groups, wherein one or more of the hydroxyl groups is replaced with groups such as a primary, secondary, or tertiary amine group, including cyclic amines and aromatic amines or the like; azido groups, wherein one or more of the hydroxyl groups is replaced with —N₃or the like; halo substituents, wherein one or more of the hydroxyl groups is replaced with a halogen atom, such as —F, —Cl, —Br, or —I; nitro groups, wherein one or more of the hydroxyl groups is replaced with —ONO₂; phosphorus-containing groups, wherein one or more of the hydroxyl groups is replaced with groups such as —OPO₃H₂, —OPO₃R₂(wherein R is alkyl or aryl), —OPO₃HR, or wherein two adjacent hydroxyl groups are replaced with groups such as —OP(O)(CH₃)O—, or the like; imidazole groups and their derivatives; pyridine groups and their derivatives; sulfur-containing functional groups, wherein one or more of the hydroxyl groups is replaced with groups such as —SCH₃, —SCH₂CH₃, —S(CH₂)₂CH₃, —SC(CH₃)₃, —OSO₃⁻Na⁺, —OCH₂SO₃⁻Na⁺, —OCH₂CH₂SO₃⁻Na⁺, —O(CH₂)₃SO₃⁻Na⁺, or the like; alcohol, aldehyde, ketone, or oxime groups; carboxylic acid groups and their derivatives; carbonate and carbamate groups; silicon, boron, or tin containing groups, wherein one or more of the hydroxyl groups is replaced with groups such as —OSi(CH₃)₃, —OSi(CH₃)₂H, —CH₂OSi(CH₃)₃, —CH₂OSi(CH₃)₂H, —OB(CH₂CH₂)₂, —CH₂OB(CH₂CH₂)₂, —CH₂OSn((CH₂)₃CH₃)₃, or the like; hydroxyalkyl groups, such as hydroxy ethyl groups, hydroxypropyl groups, or the like; or any other suitable substituent.

[0164] In another embodiment, substituent or substituents in the cyclodextrin molecules are bonded to an oxygen atom in a ring glucose unit. For example, the substituent can be an alkyl radical, desirably having up to about six carbon atoms. Another example of such a substituent has the formula —(CH—CHR¹—O—)_n—H wherein R¹is selected from the class consisting of hydrogen and alkyl groups having up to about six carbon atoms. In the above formula, n is a small whole number having a value up to about six; desirably, n is equal to 1. Preferred substituents of this type are hydroxyethyl and hydroxypropyl.

[0165] Yet another type of substituent on the cyclodextrin is a bridging group that links two cyclodextrin moieties. The bridging groups have the formula —CHR¹—CHOH—CHR¹— wherein R¹has the same significance as above. In these polymeric cyclodextrins, the number of cyclodextrin rings so bridged is from two to about six. In other words, there can be two cyclodextrin rings linked by the bridging group, or there can be three of the rings linked by two bridging groups, and so on, such that there can be six rings linked by five bridging groups. It is to be understood that higher polymers can be used in the invention if they have properties analogous to the polymers within the range given above, and the increased size or molecular weight does not confer an undesirable property to the extent that it makes the material unsuitable for use in the invention. The polymeric cyclodextrins may have substituents in addition to the group that links or bridges two cyclodextrin moieties. For example, the cyclodextrin moieties may have one or more carboxyalkyl (—R—COOH) substituents, wherein R is a lower alkylene radical having up to about 4 carbon atoms.

[0166] Cyclodextrin rings can also be bound together to form polymers by processes such as linking the cyclodextrin rings together with suitable multifunctional agents. For example, a poly-β-cyclodextrin can be formed that is crosslinked with epichlorohydrin; this material is commercially available from American Tokyo Kasei, Inc., 9211 N. Harborgate St., Portland, Oreg. 97203. It is to be understood that any method known to one of ordinary skill in the art may be used to covalently bind two or more molecular includants together. A desired embodiment is to have crosslinked γ-cyclodextrins in or on a substrate.

[0167] Cyclodextrins are commercially available from, for example, American Maize-Products Company, of Hammond, Ind. Additional information regarding cyclodextrins and modified cyclodextrins is widely available in the chemical literature, and is summarized in, for example, “Synthesis of Chemically Modified Cyclodextrins,” A. P. Croft and R. A. Bartsch, Tetrahedron,Vol. 39, No. 9, pages 1417 to 1474 (1983), the disclosure of which is totally incorporated herein by reference. Substituted cyclodextrins are also shown in the publication “Molecusol™: Your Research Solution,” Pharmetec, Inc. (1988), the disclosure of which is totally incorporated herein by reference. The hydroxypropyl substituted cyclodextrin is also suitable for the prevent invention.

[0168] Additionally, it is to be understood that the molecular includants of the present invention may have one or more of the stabilizer molecules discussed above, which may be admixed into a colorant solution, associated therewith. The term “associated”, in its broadest sense, means that the stabilizer molecule is at least in close proximity to the molecular includant. For example, the stabilizer molecule can be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, ionic bonding, hydrogen bonding, dipole-dipole interactions or the like.

[0169] The molecular includant in association with a colorant stabilizes the colorant. More particularly, the molecular includant stabilizes a colorant when it is present on or in the substrate upon which the colorant is applied.

[0170] In the embodiment where the molecular includant is present on or in the substrate, the molecular includant may be introduced onto or into the substrate by any method known to one of ordinary skill in the art, wherein the method does not destroy the molecular includant's ability to stabilize a colorant. In one embodiment, a treated substrate is one wherein the molecular includant is applied to the substrate in solution form and the substrate is subsequently dried to produce the substrate in the form it is to be utilized. Any substrate may be used, wherein the substrate does not destroy the molecular includant's ability to stabilize a colorant. A preferred substrate is paper. Any existing or future type of paper or paper products may be used in the present invention.

[0171] The molecular includant may be applied while the substrate is being manufactured, or it may be applied after the substrate has been manufactured. Where the substrate is paper, the molecular includant may be admixed into the pulp during the process of manufacturing the paper. An amount of molecular includant is admixed with the pulp so that the paper produced contains an amount of molecular includant effective to stabilize a colorant thereon. Desirably, between approximately 30 to 80% molecular includant by weight is admixed with the pulp. More desirably, between 50 to 65% molecular includant by weight is admixed with the pulp. A desirable amount of molecular includant in the final paper product is between 3% and 50% wt/wt. A more desired amount of molecular includant in the paper product is between 5 and 20%. Even more desired is between 7 and 10% of molecular includant in the paper product. Any method known in the art may be used to admix the molecular includant with the pulp, and produce the final paper product, wherein the molecular includant maintains its ability to stabilize a colorant. The above also applies to the manufacturing of wood pulp or composite substrates.

[0172] Alternatively, the molecular includant may be applied to a substrate after it has been manufactured, by dipping the substrate in a solution of the molecular includant, spraying the substrate, coating the substrate, or soaking the substrate with a solution of the molecular includant. Any method known in the art to apply a solution to a substrate and to dry the substrate may be used in the present invention so long as the molecular includant maintains its ability to stabilize a colorant. An amount of molecular includant solution is applied to the substrate so that after drying, the substrate contains an amount of molecular includant effective to stabilize a colorant thereon or therein.

[0173] Desirably, the concentration of the molecular includant solution is between 3% and 80% wt/wt. A more desired concentration is between 5 and 65%. An even more desired concentration is between 10 and 50%. A desirable amount of molecular includant in or on the treated substrate is between 1% and 50% wt/wt. A more desired amount of molecular includant in or on the treated substrate is between 3 and 25%. Even more desired is between 5 and 20% of molecular includant in or on the treated substrate. One embodiment of coating a molecular includant onto paper is fully described in Example 34.

[0174] In another embodiment, both the molecular includant and the colorant may be present within the substrate. The molecular includant and the colorant may be admixed with paper pulp, wood pulp, or monomers or oligomers, during the process of manufacturing paper, wood products, or plastics respectively. Alternatively, one of the above components can be introduced during the manufacturing process and the second component can be applied after the manufacturing process.

[0175] Examples 35 and 36 report the fade testing results of various magenta inks on treated and untreated paper. The magenta inks were studied as they tend to be the least stable of the widely used inks. More particularly, Hewlett-Packard (HP), American Ink Jet (AIJ), and Canon magenta ink jet inks, either with or without the stabilizing additives of the present invention, were printed on treated and untreated Hewlett-Packard premium paper and then exposed to an Atlas Weatherometer for a total of 77 hours. The inks containing the additives of the present invention contained 5% wt/wt of the basic fuschin imine adduct prepared in Example 7, 0.25 eq of tetramethylammonium iodide, and 2% wt/wt of hydroxyethyl β-cyclodextrin. It is to be understood that the molar equivalents of the various stabilizing compounds can be varied.

[0176] In Example 35, the treated paper was coated with γ-cyclodextrin as described in Example 34, such that the treated paper contained 7% wt/wt of the γ-cyclodextrin. After 77 total hours of exposure the change of color is measured and the ΔE* values compared. The ΔE* values reported in Example 35 for the HP and AIJ inks show that the molecular includant is an effective colorant stabilizer without the presence of additional stabilizing additives. More particularly, the ΔE* value for HP ink with no additives on untreated paper is 64, whereas the value for HP ink with no additives on cyclodextrin coated paper is 31.5. The ΔE* value for AIJ ink with no additives on untreated paper is 37, whereas the value for AIJ ink with no additives on cyclodextrin treated paper is 13.7

[0177] Additionally, the ΔE* values reported in Example 35 for the HP inks shows that the additives are an effective colorant stabilizer without the presence of the molecular includant in the paper. More particularly, the ΔE* value for HP ink with additives on untreated paper is 25.0, whereas the ΔE* value for HP ink with no additives on untreated paper is 64.0.

[0178] The ΔE* values reported in Example 35 also show that the molecular includant treated paper with the additive-containing ink yields unexpectedly superior colorant stabilization results. More particularly, the ΔE* value for HP ink with no additives on untreated paper is 64, with no additives on treated paper is 31.5, with additives on untreated paper is 25.0, and with additives on treated paper is 14.7. Accordingly, the ΔE* values show that although the additives alone stabilize the HP and AIJ inks, and treated paper alone stabilizes the HP and AIJ inks, the most lightfast colorant is stabilized by being associated with the additives in the solution and being printed on the treated paper.

[0179] In Example 36, three types of treated paper were studied along side of an uncoated paper. More particularly, HP Premium Ink Jet paper was treated with a 50% γ-cyclodextrin solution, a 20% sodium thiosulfate solution, or a 20% γ-cyclodextrin/10% sodium thiosulfate solution. The uncoated paper that was also studied is Kimberly-Clark Bright White paper. After printing, and exposure in the Atlas Weatherometer for 77 hours, the ΔE* values were measured.

[0180] The ΔE* values reported in Example 36 also show that although the additives alone stabilize the HP and AIJ inks, and treated paper alone stabilizes the HP and AIJ inks, the most lightfast colorant is stabilized by being associated with the additives in the solution and being printed on the treated paper.

[0181] With respect to the Bright White paper stabilization results reported in Example 36, these results are not readily comparable to the stabilization results obtained regarding the HP Premium paper. More particularly, most ink jet papers are coated so that the ink is not absorbed into the fibers of the paper and instead remains on the surface of the paper. The coated paper thereby produces a superior ink jet printing quality. The HP Premium paper is an example of such a coated paper.

[0182] In contrast, the Kimberly-Clark Bright White paper is not a coated paper. Accordingly, when an ink is printed thereon, the ink is wicked or absorbed into the bulk of the fibers of the paper, and does not remain on the surface of the paper, thereby yielding a different quality of printing. Although not wanting to be bound by the following, it is theorized that the ink that is absorbed into the uncoated paper is protected from degradation from light by the fibers of the paper. In contrast, inks that are printed on coated paper remain on the surface of the paper and receive no protection from the fibers of the paper. Accordingly, the stability and quality of printing of inks that are printed on an uncoated paper cannot be compared directly to inks that are printed on coated paper.

[0183] Reducing Agent

[0184] In the embodiment where the treated substrate contains a reducing agent, the reducing agent may be, but is not limited to, sodium thiosulfate (Na₂S₂O₃), sodium sulfite (Na₂SO₃), cysteine, sodium nitrite, sodium phosphite, sodium citrate, citric acid, ascorbic acid, boron hydride, dithionite, hydrazine, thiourea-dioxide, hydrogen sulphite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodium trithionite, and polyhydric phenols. A desired reducing agent is sodium thiosulfate.

[0185] The reducing agent in association with a colorant stabilizes the colorant. The reducing agent stabilizes a colorant when it is present on or in the substrate upon which the colorant is applied, or when it is admixed with the colorant prior to its application to the substrate. Also, the reducing agent may be present both on or in the substrate upon which the colorant is applied and admixed with the colorant prior to its application. Additionally, the reducing agent may be applied to the colorant after the colorant has been applied to a substrate.

[0186] In the embodiment where the reducing agent is present on or in the substrate, the reducing agent may be introduced onto or into the substrate by any method known to one of ordinary skill in the art, wherein the method does not destroy the reducing agent's ability to stabilize a colorant. The reducing agent may be applied while the substrate is being manufactured, or it may be applied after the substrate has been manufactured. It is to be understood that when a reducing agent is present on or in a substrate in the form it is to be utilized, the substrate is referred to as a “treated substrate”. In one embodiment, a treated substrate is one wherein the reducing agent was applied to the substrate in solution form and the substrate has been subsequently dried to produce the substrate in the form it is to be utilized.

[0187] Any substrate may be used, wherein the substrate does not destroy the reducing agent's ability to stabilize a colorant. As stated above, the substrate may be, but is not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, or any other substrate that would benefit from having a stabilized colorant thereon. A preferred substrate is paper. Any existing or future type of paper may be used in the present invention, including, but not limited to, newsprint, coated wood containing paper, super calendared paper, fine paper, paperboard, and ink jet paper.

[0188] Where the substrate is paper, the reducing agent may be admixed into the pulp during the process of manufacturing the paper. An amount of reducing agent is admixed with the pulp so that the paper produced contains an amount of reducing agent effective to stabilize a colorant thereon. Desirably, between approximately 2 to 50% reducing agent by weight is admixed with the pulp. More desirably, between 3 to 30% reducing agent by weight is admixed with the pulp. A desirable amount of reducing agent in the final paper product is between 1% and 50% wt/wt. A more desired amount of reducing agent in the paper product is between 2 and 20%. Even more desired is between 3 and 10% of reducing agent in the paper product. Any method known in the art may be used to admix the reducing agent with the pulp, and produce the final paper product, wherein the reducing agent maintains its ability to stabilize a colorant. The above also applies to the manufacturing of wood pulp or composite substrates.

[0189] Alternatively, the reducing agent may be applied to a substrate after it has been manufactured, or in its final form, by dipping the substrate in a solution of the reducing agent, spraying the substrate, coating the substrate, or soaking the substrate with a solution of the reducing agent. Any method known in the art to apply a solution to a substrate and to dry the substrate may be used in the present invention so long as the reducing agent maintains its ability to stabilize a colorant. An amount of reducing agent solution is applied to the substrate so that after drying, the substrate contains an amount of reducing agent effective to stabilize a colorant thereon or therein.

[0190] Desirably, the concentration of the reducing agent solution is between 1% and 50% wt/wt. A more desired concentration is between 3 and 40%. An even more desired concentration is between 5 and 20%. A desirable amount of reducing agent in or on the treated substrate is between 1% and 50% wt/wt. A more desired amount of reducing agent in or on the treated substrate is between 2 and 20%. Even more desired is between 3 and 10% of reducing agent in or on the treated substrate. One method of coating a substrate with a reducing agent is fully described in Example 34.

[0191] In another embodiment, both the reducing agent and the colorant may be present within the substrate. The reducing agent and the colorant may be admixed with paper pulp, wood pulp, or monomers or oligomers, during the process of manufacturing paper, wood products, or plastics respectively. Alternatively, one of the above components can be introduced during the manufacturing process and the second component can be applied after the manufacturing process.

[0192] In yet another embodiment, the colorant and reducing agent are admixed in one solution and applied to a substrate simultaneously. For example, a colorant and an amount of reducing agent effective to stabilize the colorant can be in an ink jet ink cartridge in an ink jet printer. It is to be understood that any commercially available ink can be admixed with a reducing agent to stabilize the colorant therein. Desirably, the concentration of the reducing agent in ink is between 1 and 50% by weight. A more desired concentration is between 3 and 40%. An even more desired concentration is between 5 and 20%.

[0193] Examples 30 and 31 report the fade testing results of Hewlett Packard yellow ink printed on sodium thiosulfate treated paper and untreated paper. More particularly, yellow Hewlett Packard ink was printed on untreated paper and paper that had been dipped in a 10% wt/wt aqueous sodium thiosulfate solution and then dried. The papers were then exposed to an Atlas Weatherometer for a total of 51 hours. Visual and color measurements (ΔE*) show that the treated paper reduces the fade of the yellow ink. In particular, the ΔE* values after 24 hours were 28.33 for the untreated paper, and 2.29 for the treated paper. The ΔE* values after 51 hours were 54.96 for the untreated paper, and 12.08 for the treated paper. Accordingly, the ΔE* values indicate little or no color change of the yellow ink on the treated paper over 51 the hours of exposure. These ΔE* values therefore show that the reducing agent is an effective colorant stabilizer.

[0194] Although the reducing agent alone stabilizes a colorant, it is also desirable that the reducing agent be utilized with one or more of the above stabilizers. Example 29 reports the fade testing results of Hewlett Packard magenta ink admixed with various combinations of stabilizing compounds of the present invention printed on treated and untreated paper. More particularly, three molar equivalents of the triiodophenol sugar produced in Example 25, four molar equivalents of the trimethylphenol sugar produced in Example 23, and two molar equivalents of sodium iodide were admixed with HP magenta ink having already admixed therein 5% by weight β-hydroxyethyl cyclodextrin. This admixture is the additive-containing ink. It is to be understood that the molar equivalents of the various stabilizing compounds can be varied.

[0195] The magenta additive-containing ink or the commercially available magenta Hewlett Packard ink (control) was printed on untreated paper and paper that had been dipped in a 10% wt/wt aqueous sodium thiosulfate solution and then dried (the treated paper). The papers were then exposed to an Atlas Weatherometer for a total of 15 hours. Visual and color measurements (ΔE*) show that the control ink on untreated paper faded the most, the additive-containing ink on untreated paper faded less, and the additive-containing ink on treated paper barely faded at all, and faded the least. In particular, the ΔE* values are as follows: 34.24 for control ink on untreated paper; 20.53 for additive-containing ink on untreated paper; and 11.09 for additive-containing ink on treated paper. Accordingly, the ΔE* values show that although the additives alone stabilize the magenta colorant, the reducing agent in the paper further stabilizes the colorant in the presence of these additives.

[0196] Additionally, the substrate itself may be treated with one or more of the above reducing agents, one or more of the above molecular includants, or combinations thereof. In one embodiment, the substrate is treated with both a reducing agent and a molecular includant. Desirably, the reducing agent is sodium thiosulfate and the molecular includant is γ-cyclodextrin.

[0197] It is most desirable to treat a substrate with a reducing agent when the ink to be printed thereon is relatively pure. Although not wanting to be limited by the following, it is theorized that if ink containing a relatively substantial amount of impurities is printed on reducing agent-treated paper, the reducing agent will react with the impurities thereby decreasing its color stabilizing properties.

[0198] It has been unexpectedly discovered that the presence of a reducing agent in paper decreases the amount of yellowing that occurs on the paper upon exposure to the radiation. Example 28 reports the testing of treated and untreated paper for reduction of yellowing. More particularly, sheets of paper were dipped in the following: (1) a sodium iodide and sodium thiosulfate solution; (2) a sodium iodide solution; or (3) a sodium thiosulfate solution, and then dried. The above sheets and control sheets (which untreated) were placed into an Atlas Weatherometer overnight. The results are as follows: the sheets treated with solution (1) turned yellow; the sheets treated with solution (2) turned dark yellow; the sheets treated with solution (3) did not change, and remained white; and the control sheets turned a very pale yellow.

[0199] Example 28 illustrates that one of the colorant stabilizers of the present invention, namely, sodium iodide, increases the yellowing of paper. In contrast, the presence of the reducing agent, sodium thiosulfate, inhibits the yellowing of paper. Further, the presence of the reducing agent decreases the amount of yellowing resulting from the sodium iodide.

[0200] The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.

Example 1

[0201] Preparation of the Imine Adduct

[0202] To a 500 ml round bottomed flask is added 10.0 g chalcone (Aldrich), 8.3 g 2-amino benzene sulfonic acid (Aldrich), 200 ml of absolute ethanol, and 3 drops of dimethylamino ethanol (Aldrich). The reaction mixture is refluxed for one hour after which the solvent is removed to yield a pale yellow crystalline solid. The yield is 16.5 grams (95%). The reaction is represented as follows:

Example 2

[0203] Preparation of Triiodophenolate Sodium Salt

[0204] To 25 g of triiodophenol (Aldrich) in a 250 ml round bottomed flask is added 100 ml diethyl ether. 52.5 ml of 1 M sodium hydroxide (Fisher) is then added and the solution is stirred for 1 hour. The mixture is then rotoevaporated under reduced pressure to yield an off-brown solid which is used without further purification.

Example 3

[0205] Effect of Triiodophenolate Sodium Salt and Triiodophenol on Degradation of Magenta Dye

[0206] 1.5 equivalents to dye of triiodophenolate sodium salt from Example 2 or 1.5 equivalents of triiodophenol is added to 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The sample is then exposed for 10 minutes to a fusion lamp (Fusion UV Curing Systems Corp., Rockville, Md., Model F300+D-bulb) having a water cooled Pyrex filter. All absorbency measurements in these Examples were made on a Perkin-Elmer UV/VIS spectrophotometer (Perkin-Elmer Corporation, Norwalk, Conn., Model LAMBDA-14P). The results are shown in the following table.

Example 4

[0207] Effect of Sodium Iodide on Degradation of Magenta Dye

[0208] 10 and 2 equivalents of sodium iodide are added respectively to two aliquots of 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The sample is then exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results are shown in the following table.

Example 5

[0209] Effect of Imine Adduct on Degradation of Magenta Dye

[0210] 1.5 equivalents of the imine adduct from Example 1 is added to 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The sample is then exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results are shown in the following table.

Example 6

[0211] Effect of Imine Adduct on Degradation of Cyan Dye

[0212] 4 equivalents or 1.5 equivalents to dye of the imine adduct from Example 1 is added to 5 g of standard Hewlett Packard cyan ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 C). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The samples are then exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results are shown in the following table.

Example 7

[0213] Preparation of the Imine Adduct of Basic Fuschin

[0214] A solution of 5.0 g basic fuschin (Aldrich) and 3.2 g chalcone (Aldrich) in 300 ml of absolute ethanol with 3 drops of dimethylamino ethanol is refluxed for 1 hour after which the solvent is removed to yield a green crystalline powder. The powder is placed under reduced pressure for 1 hour. The reaction is summarized as follows, wherein the product is referred to as “chalcone fuschin imine”:

Example 8

[0215] Effect of Basic Fuschin Imine Adduct on Degradation of Cyan Ink

[0216] As a control, basic fuschin dye (Aldrich) is dissolved in water (10% wt/wt) and applied to an HP transparency. The imine adduct from Example 7 is dissolved in water (10% wt/wt). 2% (wt/wt) to dye of the imine adduct from Example 7 is added to 5 g of standard Hewlett Packard cyan ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 C). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The sample is then exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results are shown in the following table.

Example 9

[0217] Effect of Iodide Salts on Degradation of Magenta Dye

[0218] 10 molar equivalents of sodium iodide, potassium iodide or tetramethylammonium iodide ((CH₃)₄NI) to dye are added to 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The samples is exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results are shown in the following table.

Example 10

[0219] Effect of Imine Adduct on Degradation of Magenta Dye Under a Xenon Lamp

[0220] 2 molar equivalents of the imine from Example 1 to dye is added to 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The sample is then exposed for 4.5 hours to a xenon lamp (Universal Systems, Inc., Azuza, Calif., 1000 Watt Short-Arc Lamp, Model LPS-255HR,). The results are shown in the following table.

Example 11

[0221] Effect of the Combination of Triiodophenol and Tetramethylammonium Iodide on Degradation of Magenta Dye Under a Fusion Lamp

[0222] 2 molar equivalents of triiodophenol (Aldrich) to dye and 0.5 equivalents of (CH₃)₄NI are added to 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The samples are exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The absorbency of the transparency at zero time is 0.95 and after 10 minutes of exposure to the fusion lamp, the absorbency is 0.86 showing good stabilizing activity.

Example 12

[0223] Effect of Triiodophenol on Degradation of Magenta Dye Under a Fusion Lamp

[0224] 2 molar equivalents of triiodophenol (Aldrich) to dye is admixed with 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The samples are exposed for 10, 20 and 30 minutes to a fusion lamp having a water cooled Pyrex filter. The results of the test are shown in the following table:

Example 13

[0225] Effect of the Combination of the Imine Adduct of Basic Fuschin and Sodium Iodide on Degradation of Magenta Dye Under a Fusion Lamp

[0226] 5% wt/wt of the imine adduct of basic fuschin from Example 7 and 1.5 equivalents of sodium iodide are admixed with 5 g of standard Hewlett Packard magenta ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The sample is exposed for zero and 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results of the test are shown in the following table:

Example 14

[0227] Effect of the Combination of the Triiodophenol and Tetramethylammonium Iodide on Degradation of Cyan Dye Under a Fusion Lamp

[0228] 2 equivalents of triiodophenol (Aldrich) and 0.75 equivalents of (CH₃)₄NI are added to 5 g of standard Hewlett Packard cyan ink jet ink formulation (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 C). 2% (wt/wt) of ethyl hydroxy β-cyclodextrin is added to the ink samples. The sample is drawn down on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A). The samples is exposed for 10 minutes to a fusion lamp having a water cooled Pyrex filter. The results of the test are shown in the following table:

Example 15

[0229] Effect of Stabilizers on the Viscosity Ink

[0230] A {fraction (1/16)} inch hole is drilled in a Hewlett-Packard magenta ink cartridge and a syringe is used to remove the ink. 2 equivalents of triiodophenol and 2 % wt/wt of ethyl hydroxy β-cyclodextrin are added to the ink sample and thoroughly mixed. The admixture is then put back into the cartridge using the syringe. An HP 1200C printer is used and 20 to 30 sheets are printed to get the cartridge to print fully. The viscosity is compared to control (untreated) ink by placing it in a burette and measuring volume poured from the cartridge in 10 seconds. Each value is the result of two pourings. The following table shows that the treated ink had approximately the same viscosity as the control ink.

Example 16

[0231] Fade Test on Ink from Example 15

[0232] The cartridge prepared in Example 15 is used to print on a transparency (Hewlett-Packard, Palo Alto, Calif., Cat. No. HPC 3834A) so that a square inch of ink gives an absorbency reading of between 0.85 and 0.95. The square is then cut out and exposed to a fusion lamp having a water cooled Pyrex filter. The results of the test are shown in the following table:

Example 17

[0233] Effect of Triiodophenol and Tetramethylammonium Iodide on Ink

[0234] A hole is drilled in a Hewlett-Packard magenta ink cartridge (Hewlett Packard, Palo Alto, Calif., Part No. HP 51640 M) and a syringe is used to remove the ink. 2 equivalents of triiodophenol and 0.5 equivalents of (CH₃)4NI and 2% wt/wt of ethyl hydroxy β-cyclodextrin is added to the ink sample and thoroughly mixed. The admixture is then put back into the cartridge using the syringe. The loaded cartridge is then placed in a HP 1200C printer and 20 pages are printed to stabilize the cartridge. Squares are then printed on transparencies according to Example 16. The squares are then cut out and exposed to a fusion lamp having a water cooled Pyrex filter. The results of the test are shown in the following table:

[0235] No leakage or printing problems are observed and the cartridge is used to print 205 pages with no problems.

Example 18

[0236] Cartridges are prepared according to Example 15 and printed on transparencies according to Example 16. The squares are exposed to xenon lamp radiation with a Pyrex/water filter. The UV absorption is determined at the indicated times. The results of the test are shown in the following table:

Example 19

[0237] Examples of Compounds that did not Significantly Stabilize Dyes

[0238] Using protocols similar to those described in the previous examples, the following compounds were tested for their ability to stabilize the dyes in ink jet inks: 2,4,6-triiodobenzoic acid, sodium salt, β-carotene, 3,4-didehydroretinol (Vitamin A), ascorbic acid, 4-iodobenzoic acid, selenium EDTA complex and TINUVIN 936 (Ciba-Geigy Corporation). None of these representative compounds significantly stabilized any of the dyes tested.

Example 20

[0239] Representative Combinations of Colorant Stabilizers

[0240] The following table represents various combinations of the desired colorant stabilizers that can be used to stabilize dyes. The particular combination that will be used will depend upon the final formulation of dye solution. The following table is not meant to be a comprehensive representation of all possible combinations but is only meant to show several possible combinations.

[0241] NaI=sodium iodide (NI)

[0242] (CH₃)₄NI=tetramethylammonium iodide (TI)

[0243] CD=cyclodextrin (CD)

[0244] basic fuschin imine adduct (BFI)

[0245] =sulfonic acid imine adduct (ASI)

[0246] =triiodophenol (TIP)

[0247] triiodophenol covalently bound to ethylhydroxy β-cyclodextrin. n=3 (TIP-CD)

[0248] sulfonic acid imine adduct covalently bound to ethylhydroxy β-cyclodextrin. n=3 (ASI-CD)

[0249] amino sulfonic acid (ASA)

Example 21

[0250] Preparation of Tosyl Sugar

[0251] To a 500 ml round bottom flask fitted with a magnetic stirrer and condenser is placed 75 g of 1,2-o-isopropylidene-D-glucofuranose (Aldrich) and 200 ml of anhydrous pyridine (Aldrich). The flask is cooled in an icebath and then 64.8 g of p-toluene sulfonyl chloride (Aldrich) is added. The mixture is stored overnight and allowed to warm to room temperature. The solvent is removed under reduced pressure, the oil redissolved in ether and washed with saturated copper sulfate solution, dried with MgSO₄, and the solvent removed to yield a light yellow viscous oil. The yield is 108.1 g (85%). The reaction is summarized as follows:

[0252] The resulting reaction product has the following reaction parameters:

[0253] 1H NMR [DMSO-d₆] 7.5-8.8 (m, Tosyl-Aromatic Hs), 1.2-1.6 (m, sugar's ketal CH₃s)

Example 22

[0254] Preparation of Trimethylphenol Sugar

[0255] To a 500 ml three-necked flask fitted with a magnetic stirrer, condenser and gas-inlet tube being continuously flushed with argon, 20.0 g of 2,4,6-trimethylphenol (Aldrich) and 150 ml of dry tetrahydrofuran (“THF”) is placed into the flask. 4.2 g of sodium hydride is slowly added over 30 minutes and the gas evolution allowed to subside. The reaction mixture is stirred for 30 minutes after which 55.1 g of the tosyl sugar prepared in Example 21 is added in 50 ml of THF. The reaction mixture is stirred overnight and then refluxed for 60 minutes. The reaction mixture is then filtered and the solvent removed under reduced pressure to yield a brown oil The oil is then dissolved in 200 ml of ether and 100 ml of 2N sodium hydroxide solution and the mixture stirred for one hour. The organic layer is then separated, dried with MgSO₄, and the solvent removed to yield a pale yellow oil. The yield is 32.1 g (62%). The reaction is summarized as follows:

[0256] The resulting reaction product, (3aR, 6S, 6aR)-Tetrahydro-6-hydroxy-α-[(mesityloxy)methyl]-2,2-dimethylfuro[2,3-d]-1,3-dioxole-5-methanol, had the following physical parameters:

[0257] 1H NMR [DMSO-d₆] key peaks: 7.3-6.8 (m), 4.8-3.7 (m), 2.2-2.5 (m), 1.5-1.7 (m) ppm. Mass Spectrum: m/e: 338, 323, 281, 263, 265, 208, 203, 178, 149, 136, 121, 91, 73, 69.

Example 23

[0258] Removal of Ketal Group

[0259] To a three necked flask fitted with a gas inlet and outlet and magnetic stirrer, is placed 20.0 g of the trimethylphenol sugar produced in Example 22 and 200 ml of anhydrous THF. Dry HCl gas (Matheson) is bubbled into the solution until the reaction mixture has a pH of 5-3 on moist Universal Indicator paper. The reaction was stirred at room temperature for one hour and the solvent removed under reduced pressure to yield a light brown oil The oil was found to be highly water soluble. The reaction is summarized as follows:

[0260] The resulting reaction product, (2S, 3R, 4R)- Tetrahydro-5-[1-hydroxy-2-(mesityloxy) ethyl]-2,3,4-furantriol, had the following physical parameters:

[0261] 1H NMR [DMSO-d₆] showed loss of ketal CH₃groups at 1.5 to 1.7 ppm.

Example 24

[0262] Preparation of Triiodophenol Sugar

[0263] Into a three-necked round bottom flask fitted with a magnetic stirrer, gas inlet, and condenser, is placed 20 g 2,4,6-triiodophenol and 200 ml of dry THF. The flask is cooled in an ice bath and 1.2 g of sodium hydride added slowly over 30 minutes. The mixture is then stirred for 30 minutes and then 15.6 g of tosyl sugar from Example 21 added in 50 ml of THF. The reaction is then heated to reflux overnight. The reaction mixture is then filtered and the solvent removed to yield a dark brown oil. The oil is then stirred in 200 ml of diethyl ether and 200 ml of 2N sodium hydroxide. The organic layer is then separated, dried with MgSO₄, and the solvent removed under reduced pressure to yield a pale yellow oil. The yield is 21.3 g (76%). The reaction is summarized as follows:

[0264] The resulting reaction product, (3aR, 6S, 6aR)-Tetrahydro-6-hydroxy-2,2-dimethyl-α-[(2,4,6-triiodophenoxy)methyl]furo [2,3-d]-1,3-dioxole-5-methanol, has the following physical parameters:

[0265] Mass Spectrum: m/e: 529, 460, 431, 402, 358, 289, 275, 231, 145, 129, 73.

Example 25

[0266] Removal of Ketal Group

[0267] To a 250 ml three necked round bottom flask fitted with gas inlet and outlet is placed 10.0 g of triiodophenol sugar produced in Example 24 and 150 ml of anhydrous THF. Dry HCl gas is bubbled into the reaction mixture until the solution has a pH of 3-5 on moist Universal Indicator paper (Fisher). The reaction mixture is then evaporated under reduced pressure to yield 8.8 g (96%) of a pale yellow oil. The reaction is summarized as follows:

[0268] The resulting reaction product, (2S, 3R, 4R)-Tetrahydro-5-[1-hydroxy-2-(2,4,6-triiodophenoxy)ethyl]-2,3,4-furantriol, has the following physical properties:

[0269] Mass Spectrum: m/e: 529, 460, 347, 231, 145, 129, 73

Example 26

[0270] Fade Testing of Hewlett Packard Magenta Ink with Additives Prepared in the Examples Above on Neenah Bond Paper

[0271] Three Hewlett Packard HP5 1640M Magenta ink cartridges (Palo Alto, Calif.) are drilled with a ⅛ inch drill and the ink removed via syringe into a 250 ml Erlenmeyer flask. 4.8 g (2% wt/wt) β-hydroxyethyl cyclodextrin (American Maize) is added to the 96.7 g ink and the mixture shaken for 10 minutes to dissolve and disperse the cyclodextrin. Then 8.7 g trimethylphenol sugar (3 molar equivalents, or “eq”) produced in Example 23, 19.3 g of triiodophenol sugar (4 eq) produced in Example 25, and 5.6 g of NaI (2 eq), are added to the mixture and shaken and sonicated for 20 minutes. The resultant mixture is then divided evenly into three aliquots, and one aliquot each of the resultant mixture is reintroduced into each of the drilled ink cartridges via syringe and filtered simultaneously through a 0.45 μ filter. The cartridges are then placed into a Hewlett Packard 1600C printer and test sheets are printed out on Neenah Bond, Kimberly Clark Corporation. Sheets number 30-32 are generated and subjected to fade studies against control sheets as described above, except that the sheets are exposed to an Atlas Electric Devices Co. (Chicago, Ill.) Weatherometer, Model No. C135W, radiance at 0.53 watts/m²at 340 nm, wherein the black panel is at 32° C., borosilicate filters, and the humidity is 50%. Absorbency is measured after 0 and 66 hours of exposure of the control and experimental samples generated above. Absorbency is measured with a Perkin Elmer UV/Visible Spectrophotometer λ14B.

[0272] The results of the fade studies are shown in the tables below. The table below reports the fade study absorbancy results for the control sheet samples at 0 and 66 hours.

[0273] The table below reports the fade study absorbancy results for the experimental sheet samples generated as described above at 0 and 66 hours.

Example 27

[0274] Fade Testing of Hewlett Packard Magenta Ink on Transparency Sheets

[0275] The procedure of Example 26 is repeated except that the control and experimental inks are printed on Hewlett Packard Premium Transparency HPC 3834A sheets instead of on Neenah Bond paper. The control sheet absorbancy values after 66 hours are 0.09 for sample 1, and 0.02 for sample 2. The experimental absorbancy value after 66 hours is 0.79 for sample 1.

Example 28

[0276] Testing of Treated Paper for Reduction of Yellowing

[0277] The yellowing of paper is tested by dipping the paper in a solution as described below, drying the paper, and then exposing the paper in a weatherometer for 12 hours. More particularly, the paper is placed in a container to soak in the solution, hung on a line in a fumehood to drip dry, and then oven dried as described below.

[0278] Solution A Sodium Iodide+Sodium Thiosulfate

[0279] A 6.7% wt/wt sodium iodide and 10% wt/wt sodium thiosulfate solution in water is prepared. Strips of Neenah bond paper are dipped into the solution and then dried in a vacuum oven at 60° C. for 15 minutes. The paper is then placed into an Atlas Weatherometer and exposed to the following conditions for twelve hours: 0.53 W/m², 50% humidity, 32° C.

[0280] Solution B Sodium Iodide

[0281] A 6.7 % wt/wt solution of sodium iodide is prepared and Neenah bond paper strips are dipped therein, dried, and exposed in a weatherometer as described above.

[0282] Solution C Sodium Thiosulfate

[0283] A 10% wt/wt solution of sodium thiosulfate is prepared and Neenah bond paper strips are dipped therein, dried, and exposed in a weatherometer as described above.

[0284] Control

[0285] Strips of Neenah bond paper were cut and exposed in a weatherometer as described above.

[0286] The results of exposing the treated and control strips of paper are as follows: The paper treated with solution A turned yellow. The paper treated with solution B turned dark yellow. The paper treated with solution C did not change, and remained white. The control samples turned very pale yellow. Accordingly, treating paper with sodium thiosulfate reduces the amount of yellowing that occurs over time.

Example 29

[0287] Fade Testing of Hewlett Packard Inks Printed on Sodium Thiosulfate Treated Paper

[0288] This example determines if sodium thiosulfate treated paper enhances the resistance to fade of Hewlett Packard Ink admixed with the colorant stabilizers of the present invention.

[0289] Several sheets of Hewlett Packard premium ink jet paper are soaked in a 10% wt/wt aqueous solution of sodium thiosulfate, and then dried in a vacuum oven at 60° C. for 15 minutes at 0.1 mm Hg. These sheets are referred to as the “treated paper”.

[0290] The Hewlett Packard ink cartridge (magenta ink) is prepared as described above, by drilling a hole in the cartridge, removing the ink via a syringe, and placing the ink in an Erlenmeyer flask. 5% wt/wt of hydroxyethyl-β-cyclodextrin is put into the flask, and the mixture shaken for 10 minutes. Afterwards, 3 equivalents of triiodophenol sugar produced in Example 25, 4 equivalents of trimethylphenol sugar produced in Example 23, and 2 equivalents of sodium iodide are added to the mixture and shaken for 20 minutes. It is to be understood that “equivalents” above are molar equivalents to the dye in the ink. The Ink mixture is then reinjected into the ink jet cartridge via syringe with 0.45 μ filter attachment. This cartridge is referred to as the additive containing cartridge.

[0291] Test sheets are printed using control cartridges (other Hewlett Packard ink jet cartridges, including magenta, yellow, and cyan, without the above additives) and the additive containing cartridge on treated and untreated paper. More particularly, treated and untreated sheets are printed with Hewlett Packard magenta, yellow, and cyan ink cartridges that do not contain additives. Additionally, treated and untreated sheets are printed with Hewlett Packard yellow and cyan ink cartridges that do no contain additives and with the additive containing cartridge that contains magenta ink. The paper is then placed in the Atlas Weatherometer and exposed for 15 hours to the following conditions: 0.53 W/m²at 340 nm, 50% humidity, borosilicate filters, and 32° C.

[0292] The change in color is measured by the Xrite Colorimeter (Model 938, SpectroDensitometer, Grandville, Mich.) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2.

[0293] Visual and actual measurements show the control magenta ink on untreated paper faded the most, the additive-containing magenta ink on untreated paper faded less, and the additive-containing magenta ink on treated paper barely faded at all, and faded the least. More particularly, the ΔE* values are as follows:

[0294] Percentage wise, additive containing ink is 40% better in fade resistance than control ink (both on untreated paper), and additive containing ink on treated paper is 68% better in fade resistance than control ink on untreated paper, after 15 hours exposure.

[0295] Examination of the % Reflectance graphs of the samples before and after fading shows that the magenta dye does not fade or its concentration change when the additive is present in the ink and it is printed on the treated paper. However, the control clearly shows loss of the dye chromophore. In contrast, the additive system in the ink protects the loss of dye, however the ΔE* values show that the additive system yellows somewhat upon exposure to light, hence yielding the ΔE* value. The treated paper therefore decreases this yellowing of the additive thus giving the smallest ΔE* (color change) after 15 hours of exposure.

Example 30

[0296] Fade Testing of Yellow Hewlett Packard Inks Printed on Sodium Thiosulfate Treated Paper and Untreated Paper

[0297] This example determines if sodium thiosulfate treated paper enhances the resistance to fade of yellow Hewlett Packard Ink.

[0298] The papers exposed to the Atlas Weatherometer in Example 29 also had yellow and cyan squares printed thereon in boxes next to the magenta squares. Although some of the magenta squares contained the stabilizing additives, all of the yellow and cyan squares did not contain the additives.

[0299] Accordingly, yellow Hewlett Packard Ink is printed on both treated and untreated Hewlett Packard premium ink jet paper and then exposed to the Atlas Weatherometer under the conditions listed in Example 29. It is to be understood that the treated paper is soaked in a 10% wt/wt solution of sodium thiosulfate and dried in a vacuum oven under the conditions listed in Example 29.

[0300] The yellow ink on the weatherometer-exposed treated paper has little or no fading in comparison with the yellow ink on the unexposed treated paper. However, the yellow ink on the weatherometer-exposed untreated paper is substantially faded in comparison with the yellow ink on the unexposed untreated paper. Accordingly, the treated paper reduces the fade of the yellow ink in comparison to the untreated paper.

Example 31

[0301] Fade Testing of Yellow Hewlett Packard Inks Printed on Sodium Thiosulate Treated Paper and Untreated Paper

[0302] This example determines if sodium thiosulfate treated paper enhances the resistance to fade of yellow Hewlett Packard Ink.

[0303] Additional ink samples were printed of Hewlett Packard inks, including yellow ink, on treated and untreated paper using the method described in Example 29. The samples were placed in the Atlas Weatherometer under the conditions listed in Example 29, except that the samples were exposed for a total of 51 hours.

[0304] Visual and color measurements (ΔE*) show that the treated paper reduces the fade of the yellow ink. More particularly, the ΔE* values for the yellow ink are as follows:

[0305] The ΔE* values indicate little or no color change of the yellow ink on the treated paper over 51 hours.

Example 32

[0306] Fade Testing of Cyan Hewlett Packard Inks Printed on Sodium Thiosulfate Treated Paper and Untreated Paper

[0307] Samples were printed of Hewlett Packard inks, including cyan ink, on treated and untreated paper using the method described in Example 29. It is to be understood that none of the cyan inks contained the stabilizing additives listed in Example 29. The samples were placed in the Atlas Weatherometer under the conditions listed in Example 29, except that the samples were exposed for a total of 51 hours.

[0308] The treated paper had little or no effect on the fade of the Hewlett Packard cyan ink in comparison to the untreated paper. At 24 hours and 51 hours of total exposure to the Weatherometer, the cyan ink faded to a similar extent on the treated and untreated paper.

Example 33

[0309] Fade Testing of Inks Printed on Treated Paper

[0310] Fade testing of a magenta American Ink Jet ink jet formulation for a Canon printer is conducted as follows. The magenta ink is printed on cyclodextrin treated paper and sodium thiosulfate treated paper, and then exposed for 100 hours in an Atlas Weatherometer.

[0311] More particularly, approximately 10 ml of ink is removed from a small cartridge for a Canon BJC printer by use of a syringe with needle, via the wick plug. The following stabilizing additives are admixed with the magenta ink: 5% wt/wt of basic fuschin imine adduct prepared in Example 7; 0.25 eq tetramethylammonium iodide; and 2% wt/wt hydroxyethyl-γ-cyclodextrin. The ink admixture is placed back into the cartridge via syringe with a 0.45 μ filter. The first 15 to 20 sheets printed are discarded to ensure that the ink admixture is being printed on the paper to be exposed to the Atlas Weatherometer.

[0312] Sodium Thiosulfate Treated Paper

[0313] The sodium thiosulfate treated paper is prepared as follows. A stock solution of 15 g sodium thiosulfate is placed in a beaker of 150 g of water and dissolved. The solution is placed in a Pyrex oven dish and sheets of Hewlett Packard Premium ink jet paper are placed therein, one sheet at a time. After the sheet has soaked in the sodium thiosulfate solution for 3 to 4 minutes, the sheets are removed and placed in a vacuum oven which is heated to 30-32° C. and the vacuum of 0.1 torr applied for 15 to 20 minutes, producing dried sheets of paper.

[0314] By weighing a sheet before submersion in the sodium thiosulfate solution, and after the drying step, the amount of sodium thiosulfate present on or in the paper is calculated to be approximately 12% wt/wt.

[0315] Cyclodextrin Treated Paper

[0316] The cyclodextrin treated paper is prepared as follows. A 10% wt/wt solution of hydroxyethyl-γ-cyclodextrin is prepared, and sheets of Hewlett Packard Premium ink jet paper are treated as described above. By weighing a sheet before submersion in the cyclodextrin solution, and after the drying step, the amount of cyclodextrin present on or in the paper is calculated as approximately 3.4%.

[0317] A series of sheets are printed on the Canon BJC printer using the ink admixture prepared above or the commercially available ink for the printer as the control. Untreated sheets are printed (control), as well as sodium thiosulfate treated sheets and cyclodextrin treated sheets. The sheets are then exposed to light radiation for 100 hours in an Atlas Weatherometer having the following conditions: 0.54 W/m²at 440 nm irradiance; black panel temperature of 45° C.; borosilicate filters; and humidity of 55%. The color change readings (ΔE*) are measured using the X-rite meter. The results are reported below.

[0318] As can be seen above, the stabilizing molecules in the ink admixture improve the light fastness and give a slight shift in hue of the colorant therein upon exposure to radiation. However, the above data clearly shows that the stabilizing molecules in the ink, in combination with the ink being printed on the treated paper, significantly improves the colorants resistance to fade upon exposure to radiation. The cyclodextrin treated paper gave the colorant the greatest improvement in light fastness, with the sodium thiosulfate treated paper giving the colorant the second best improvement in light fastness.

Example 34

[0319] Preparation of Treated Paper

[0320] This examples describes one method of treating paper with either cyclodextrin or sodium thiosulfate. Hewlett-Packard premium ink jet paper is coated and dried to obtain flat treated paper for ink jet fade studies described in Examples 35 and 36.

[0321] More particularly, the paper is coated as follows. The paper is rolled between two rollers that are positioned on top of each other, wherein the bottom portion of the bottom roller is submersed in a solution of either cyclodextrin or sodium thiosulfate, and wherein a controlled amount of the same solution is continually dripped onto the top portion of the top roller. It is to be understood that as the paper rolls between the rollers, the paper is coated on its top surface by contact with the lower portion of the top roller which contains the solution thereon, and the solution continues to be applied to the top portion of the top roller as it rolls via contact with the paper. Additionally, as the paper rolls between the rollers, the paper is coated on its bottom surface by contact with the top portion of the bottom roller which contains the solution thereon, and the solution continues to be applied to the lower portion of the bottom roller (which is submersed in the solution) as it rolls via contact with the paper.

[0322] After the paper passes through the rollers as described above, it is rolled onto a steel, steam heated drum with a fabric flap to prevent the paper from curling as it is dried thereon.

[0323] The γ-cyclodextrin treated paper is prepared as follows. The HP premium paper is weighed prior to treatment. A 50% by weight aqueous solution of γ-cyclodextrin is prepared and applied to the top and bottom surfaces of the HP premium paper as described above. After the treated paper is dried, the paper is again weighed to yield a 7% wt/wt cyclodextrin content in or on the paper.

[0324] The sodium thiosulfate treated paper is prepared as follows. The HP premium paper is weighed prior to treatment. A 20% by weight aqueous solution of sodium thiosulfate is prepared and applied to the top and bottom surfaces of the paper as described above. After the treated paper is dried, the paper is again weighed to yield a 2% wt/wt sodium thiosulfate content on or in the paper.

[0325] These treated papers are used in the fade testing studies reported in Examples 35 and 36.

Example 35

[0326] Fade Testing of Various Magenta Inks on Treated Paper

[0327] This example reports the results of fade testing of Hewlett-Packard (HP), American Ink Jet (AIJ), and Canon magenta ink jet inks, either with or without the stabilizing additives of the present invention, on treated or untreated Hewlett-Packard Premium paper.

[0328] The inks having the stabilizing additives of the present invention are prepared as described in the above examples, wherein the ink is removed from the appropriate cartridge, mixed with the additives, shaken and then sonicated for 20 minutes, then injected into the original cartridge via syringe fitted with a 0.45 μ filter. The resultant ink contains the following additives: 5% wt/wt of the basic fuschin imine adduct prepared in Example 7; 0.25 eq of tetramethylammonium iodide; and 2% wt/wt hydroxyethyl β-cyclodextrin.

[0329] The magenta inks are printed onto HP premium paper and the treated paper prepared in Example 34. The Hewlett-Packard inks and the American Ink Jet inks are printed using a Hewlett-Packard 1600C printer and the Canon inks are printed using a BJC-600 printer.

[0330] The sheets were then placed in the Atlas Weatherometer and exposed for a total of 77 hours under the following conditions: 0.54 W/m²at 440 nm, borosilicate filters, 55% humidity, and 45° C. black panel temperature.

[0331] The change in color of the magenta ink is measured by the Xrite Colorimeter (Model 938, SpectroDensitometer, Grandville, Michigan) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2. The results are reported in the table below.

[0332] As shown above, the additives reduce fade, and when the ink containing the additives is printed on treated paper, the amount of fade is even further reduced.

Example 36

[0333] Fade Testing of Various Magenta Inks on Treated Paper

[0334] This example reports the results of fade testing of Hewlett-Packard (HP), American Ink Jet (AIJ), and Canon magenta ink jet inks, either with or without the stabilizing additives of the present invention, on treated or untreated paper. More particularly, the paper is untreated Hewlett-Packard Premium paper, Kimberly-Clark Bright White ink jet paper, or Hewlett-Packard Premium paper treated as described in Example 34. Three types of treated paper are prepared using one of the following three aqueous solutions: 50% wt/wt γ-cyclodextrin; 20% wt/wt sodium thiosulfate; or 20% wt/wt γ-cyclodextrin and 10% wt/wt sodium thiosulfate.

[0335] As stated above in Example 34, the 50% cyclodextrin treated paper has a 7% wt/wt cyclodextrin content in or on the paper, and the 20% sodium thiosulfate treated paper has a 2% wt/wt sodium thiosulfate content in or on the paper. The paper treated with the 20% wt/wt γ-cyclodextrin and 10% wt/wt sodium thiosulfate solution is weighed before and after treatment, to yield a 4 to 5% wt/wt total content of cyclodextrin and sodium thiosulfate in or on the paper.

[0336] The treated and untreated paper is printed with the additive containing inks prepared in Example 35 or with the corresponding non-additive containing inks. The HP and AIJ inks were printed from HP 1600 cartridges using an HP 1600C printer. The Canon ink was printed with a BJC-600 printer.

[0337] The sheets were then placed in the Atlas Weatherometer and exposed for a total of 77 hours under the following conditions: 0.54 W/m²at 440 nm, 55% humidity, 45° C. black panel temperature, borosilicate filters.

[0338] The change in magenta color is measured by the Xrite Colorimeter (Model 938, SpectroDensitometer, Grandville, Mich.) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2. The results are reported in the table below.

Example 37

[0339] Preparation of Heat Sealable Media Products Containing Colorant Stabilizer Additives

[0340] This example describes the preparation of heat sealable media products containing colorant stabilizing additives of the present invention. In this example, the colorant stabilizing additive is a molecular includant, such as hydroxypropyl β-cyclodextrin. Heat sealable media products provide many uses. For example, such a media product can be constructed of a substrate layer such as paper, coated with at least one polymer containing the colorant stabilizing additive of the present invention. These media products can be used as an alternative to laminating products, in order to provide a lightfast and waterfast media product.

[0341] Additionally, such media products can be heat transfer products as described for example in U.S. Pat. No. 4,863,781, U.S. Pat. No. 5,242,739 and U.S. Pat. No. 5,501,902, which are hereby incorporated by reference. Generally, heat transfer products comprise a substrate layer, such as paper, coated with at least one polymer which releases a printable material upon the application of pressure and heat. Such heat transfer products are commonly used for melt printing designs on articles of clothing, for example. Additionally, heat transfer papers have been developed specifically for transferring graphics printed with an ink jet printer.

[0342] The thermoplastic polymers coating one or both sides of the substrate layer are typically selected from polyolefins, polyesters, ethylene-vinyl acetate copolymers or nylons. Additional components include humectants, ink viscosity modifiers, weak acids, surfactants, and binders, for example.

[0343] The present invention provides that from about 2% to 20% wt/wt molecular includant may be added to the coating polymer as a colorant stabilizing additive. The example below describes the production of two such media product coatings. The following ingredients were combined to make coating Formula A:

[0344] 1) 217 parts water

[0345] 2) 35 parts styrene maleic anhydride

[0346] 3) 4.4 parts 28% solution ammonia in water

[0347] 4) 88 parts 25% solution ethylene acrylic acid (available as MICAM PRIME from Michaelman Inc.)

[0348] 5) 88 parts nylon copolymer 6/12, (available as ORGOSOL from Elf Atachem) having the formula

[0349] 6) 88 parts polyvinyl alcohol

[0350] 7) 38 parts 30% solution hydroxypropyl β-CD

[0351] All ingredients were combined in a beaker, and blended with a mechanical stirrer into a smooth white paste. The paste was then milled for further consistency.

[0352] Suitable variations of the above formula will be apparent to those skilled in the art through routine experimentation. For example, in one alternative formulation, coating Formula B, elements 1-6 were combined in the same proportions, however, 456 parts 30% solution hydroxypropyl β-CD was used instead of 38 parts. As can be seen in the results below, the higher molecular includant content Formula B coating produced a more fade resistant media product. The results support a range of colorant stabilizer additive amounts.

[0353] The media coatings were then separately applied to a substrate, HP premium paper, by drawing down with a zero draw down bar. The wet coating was then dried in a vacuum oven to produce a coated media product. Ink B3, prepared as described below, was then printed onto the samples. The ink was fused to the media coating by briefly heating at about 300 degrees Fahrenheit for about 30 seconds.

[0354] When vinyl is used as an underlying coating layer, such as in a heat transfer product, the coating can be preferably adhered thereto by the addition of an intermediate coating layer, such as 50% wt of a polyvinyl acetate and silica, mill ground for consistency.

[0355] Printed sheets of media product from this example were placed in the Atlas weatherometer and exposed for the designated number of hours under the following conditions: 0.54 W/m²at 440 nm, 55% humidity, 45° C. black panel temperature, borosilicate filters.

[0356] The change in magenta color is measured by the Xrite Colorimeter (Model 938, SpectroDensitometer, Grandville, Mich.) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2. The results are reported in the tables below.

Example 38

[0357] Preparation and Testing of Inks Containing Porphine Colorant Stabilizers

[0358] This example reports the results of fade testing of various inks, either with or without the stabilizing additives of the present invention, on treated or untreated paper. More particularly, the paper is untreated Hewlett-Packard premium paper, or treated Hewlett-Packard premium paper prepared using a solution of about 50% wt/wt hydroxypropyl γ-cyclodextrin to ink, in or on the paper in a concentration of about 5 to 15 % wt/wt solution to paper.

[0359] The stabilizing additives of this example can be porphines. Specifically, the porphines Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine (designated CuTMPS4) (available from Porphyrin Products, Inc., Logan, Utah) were used, which are represented by the following structures, respectively:

[0360] The invention provides that the metal ion Co or Cu may be used interchangeably in the porphine structures of the present invention. Additional background on the chemistry of porphines can be found in Kubat et al. “Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) Porphyrin,” Journal of Photochemistry and Photobiology A:Chemistry96 (1996) 93-97, and references cited therein, hereby incorporated by reference.

[0361] The stabilizing additive of this example can also optionally be dimethyl amino benzoic acid quat (designated DMABAQ), which can be produced as shown in the following reaction.

[0362] Into a 3 necked 500 ml. round bottomed flask fitted with magnetic stirrer and condenser was added 20 g (0.12 moles) dimethyl amino benzoic acid (Aldrich) and 100 ml. of toluene. The Dean-Stark adapter was fitted and 80 ml. of toluene (Aldrich anhydrous grade) 14.4 g (0.12 mole) thionyl chloride added and the mixture heated at reflux for 2 hours. Toluene was then distilled off as more (100 ml.) was added. 16.8 g (0.12 mole) of choline chloride (Aldrich) dried in 50 ml. of toluene (Dean Stark) was added and the mixture refluxed overnight. The solution was then filtered hot and poured into a beaker chilled in an ice bath. The DMABAQ solid was then filtered and dried in a vacuum oven at 30° overnight.

[0363] Printed sheets of paper were placed in the Atlas weatherometer and exposed for the designated number of hours under the following conditions: 0.54 W/m²at 440 nm, 55% humidity, 45° C. black panel temperature, borosilicate filters.

[0364] The change in magenta color is measured by the Xrite Colorimeter (Model 938, SpectroDensitometer, Grandville, Mich.) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2. The results are reported in the tables below.

[0365] The treated and untreated paper is printed with inks designated A1, A2, A3, A4, B1, B2, B3, B4, C1, C2, C3, and C4, prepared as follows:

[0366] The above inks were fade tested with the following results.

[0367] The A2 ink was prepared with additives as described below and fade tested on HP paper and HP γ-CD paper with the following results.

[0368] The A3 ink was prepared with additives as described below and fade tested on HP paper and HP γ-CD paper with the following results.

[0369] The inks were prepared with about 0.5% CuTPPS₄stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

[0370] Additionally, HP-1600 magenta ink was prepared with about 0.5% CuTPPS₄stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

[0371] The HP-1600 magenta ink was also prepared with about 0.5% CuTMPS₄stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

Example 39

[0372] Preparation and Testing of Inks Containing Porphine and Lanthanide Colorant Stabilizers

[0373] This example reports the results of fade testing of various inks, either with or without the stabilizing additives of the present invention, on untreated paper. More particularly, the paper is untreated QIS Photo Glossy paper.

[0374] The stabilizing additives of this example are porphines and europium salts. Specifically, the porphine Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) (available from Porphyrin Products, Inc., Logan, Utah) is used, as in Example 38 above. The europium salt, europium nitrate (designated EuN) (Strem Chemical Co., Newburyport, Mass.) is used.

[0375] A forty-eight hour accelerated fade test of various magenta ink composition was performed. A magenta control without stabilizing additives was applied to the QIS paper medium. After subjecting the ink composition and paper medium to the forty-eight hour test, ΔE* and ΔH* values were measured. Similar measurements were taken using the following ink formulations:

[0376] a) magenta+0.5 wt % CuTPPS4

[0377] b) magenta+0.05 wt % EuN

[0378] c) magenta+0.5 wt % CuTPPS4+0.05 wt % EuN.

[0379] The resulting measurements are given below.

Example 40

[0380] Preparation of Basic Fuschin Hydrazone

[0381] Another colorant stabilizer of the present invention is a basic fuschin hydrazone, prepared as follows. To a 500 ml round bottom flask, fitted with a magnetic stirrer and a heating mantle, was placed 50 g (0.46 mole) phenyl hydrazine (Aldrich), 96.3 g (0.46 mole) chalcone (Aldrich), and 300 ml. of anhydrous ethanol. The reaction mixture refluxed overnight and then cooled to room temperature. A white precipitate formed and was filtered to yield a white solid which was washed with cold ether. 128 g (93%) chalcone hydrazone was obtained. This reaction is shown below.

[0382] To a 500 ml three necked flask fitted with a condenser, Argon bubbles and a magnetic stirrer, was placed 20 g (0.09 mole) 4,4′-diamino benzophenone (Aldrich), 27.1 g (0.09 mole) chalcone hydrazone (produced above), 10.1 g phosphorous oxy chloride (Aldrich) and 200 ml of dried dioxane. The mixture was refluxed for two days to yield a red solution. The reaction mixture was chilled in an ice bath and the red precipitate filtered to yield 35.2 g (78%). Addition of hexane to the solution generated an extra 3 g The compound was purified by neutralization from 3% ethanol in 97.1% chloroform. It was also run down a column (silica gel) with 1% ethanol in CHCl₃to elute impurities, then the product was eluted with 10% ethanol in chloroform. This reaction is shown below.

Example 41

[0383] Preparation and Testing of Inks on Paper Containing Benzophenone Colorant Stabilizer Additives

[0384] This example reports the results of fade testing of magenta ink jet inks on Hewlett-Packard premium paper containing another stabilizing additives of the present invention. In particular, the additive of this example is a benzophenone, of the general formula:

[0385] wherein R represents any substituents which permit the benzophenone to function as a colorant stabilizer.

[0386] More specifically, in this example the benzophenone derivative is 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid (designated HMBPD, or simply U) (available from Lancaster Synthesis Ltd., Windham, N.H.), represented by the following structure:

[0387] In addition, the colorant stabilizing additive can be a molecular includant, such as a cyclodextrin. The paper containing the additives was prepared as follows:

[0388] Pre-complexation of Additive U with β-CD

[0389] 5.0 g (0.02 mole) of 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid (additive U), 27.2 g (0.02 mole) β-cyclodextrin and 136 ml water was placed in a beaker and stirred on a hot-plate stirrer. The suspension was heated to 65° C. at which point the mixture became a clear solution.

[0390] Paper Coating Solution

[0391] 0.7 ml of SURFYNOL 420 surfactant and 30.0 g (0.02 mole) γ-CD was then added to the above solution and stirred while maintaining 65° C. The heated clear solution was used to coat the HP Premium ink jet paper. The surface tension of the heated solution was 48-52 dyne/cm.

[0392] Coating Papers Procedure

[0393] Pre-weighed Hewlett-Packard Premium ink jet paper #51634Y was placed on a stack of 20 sheets of NEENAH BOND® paper and a draw-down bar placed at the top of the paper. Using a Pasteur pipette, the hot additives solutions were placed on the paper at the edge of the draw-down bar. The draw-down bar was then drawn-down on the paper sheet with light pressure to yield a wet film. The paper was then placed in a vacuum oven and dried under 0.1 mm Hg vacuum at 35° C. for 20 minutes. The dried paper was re-weighed and the add-on calculated. The sheets were then used directly for printing.

[0394] For testing, an Atlas Ci35 weatherometer controlled irradiance exposure system was used which provides high intensity daylight simulation with xenon source set at an average temperature of 63° C., an irradiance of 1.10 W/m²/nm (at 420 nm), and a humidity of 30% in an industry standard test environment (ASTM G-26 Method 3).

[0395] Color measurement was determined by an X-Rite 938 Spectrodensitometer measurement and storage of full spectral curves. Three measurements of each sample with averaging were performed with automatic calculation of CIELAB values. CIELAB calculated for D-50 standard lighting conditions. The results are reported in the table below.

[0396] Additional tests yielded the following results.

[0397] Additional tests yielded the following results.

[0398] Additional tests yielded the following results.

[0399] The results suggest that pre-complexation of Additive U with β-CD gives superior results than when added separately. Pre-complexation of Additive U with β-CD followed by mixing with γ-CD gives maximally superior results. Additive U when coated on HP paper without cyclodextrin provides some improvement. γ-CD and β-CD applied separately and together provides some improvement in light-fastness.

[0400] Having thus described the invention, numerous changes and modifications thereof will be readily apparent to those having ordinary skill in the art, without departing from the spirit or scope of the invention.

Claims

What is claimed is:

1. An ink composition comprising a mixture of

wherein

a) a colorant;

b) a colorant stabilizer; and

c) a liquid vehicle;

wherein the colorant stabilizer comprises a compound having the following general formula:

R₁is iodine, or an alkyl group having between 1 and 5 carbon atoms;

R₂is an iodine, or an alkyl group having between 1 and 5 carbon atoms;

R₃is iodine, or an alkyl group having between 1 and 5 carbon atoms; and

R₄is a sugar, a polyhydroxy compound, a sulfonic acid salt compound, a carboxylic acid salt compound, or a polyether compound.

2. The ink composition of claim 1, wherein the sugar comprises glucose, fructose, a polyether sugar, a monosaccharide, a polysaccharide, or a cyclodextrin.

3. The ink composition of claim 2, wherein the cyclodextrin comprises α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin, sulfated β cyclodextrin and sulfated γ-cyclodextrin.

4. The ink composition of claim 1, wherein R₁, R₂and R₃comprise iodine or a methyl group.

5. The ink composition of claim 1, wherein the colorant stabilizer has one of the following formulae:

6. The ink composition of claim 1, wherein the colorant stabilizer has one of the following formulae:

7. The ink composition of claim 1, wherein the colorant stabilizer has the following formula:

8. The ink composition of claim 1, wherein the colorant stabilizer has one of the following formulae:

wherein n is an integer from 1 to 21 and CD represents a cyclodextrin.

9. The ink composition of claim 1, further comprising a molecular includant.

10. An ink set comprising two or more inks, wherein at least one ink of the ink set comprises the ink composition of claim 1.

11. A substrate having thereon the ink composition of claim 1.

12. A colorant stabilizing composition comprising at least one stabilizing agent, the at least one stabilizing agent comprising a compound having the following general formula:

wherein

R₁is iodine, or an alkyl group having between 1 and 5 carbon atoms;

R₂is an iodine, or an alkyl group having between 1 and 5 carbon atoms;

R₃is iodine, or an alkyl group having between 1 and 5 carbon atoms; and

R₄is a sugar, a polyhydroxy compound, a sulfonic acid salt compound, a carboxylic acid salt compound, or a polyether compound.

13. The colorant stabilizing composition of claim 12, wherein the sugar comprises glucose, fructose, a polyether sugar, a monosaccharide, a polysaccharide, or a cyclodextrin.

14. The colorant stabilizing composition of claim 13, wherein the cyclodextrin comprises α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin, sulfated β cyclodextrin and sulfated γ-cyclodextrin.

15. The colorant stabilizing composition of claim 12, wherein R₁, R₂and R₃comprise iodine or a methyl group.

16. The colorant stabilizing composition of claim 12, wherein the colorant stabilizer has one of the following formula:

17. The colorant stabilizing composition of claim 12, wherein the colorant stabilizer has one of the following formulae:

wherein n is an integer from 1 to 21 and CD represents a cyclodextrin.

18. The colorant stabilizing composition of claim 12, further comprising a molecular includant.

19. An ink comprising the colorant stabilizing composition of claim 12.

20. A substrate having thereon the colorant stabilizing composition of claim 12.

21. The colorant stabilizing composition of claim 12, further comprising a colorant.

22. A colorant stabilizing composition comprising at least one stabilizing agent, the at least one stabilizing agent comprising a compound having the following general formula:

wherein

R₁is iodine, or an alkyl group having between 1 and 5 carbon atoms;

R₂is an iodine, or an alkyl group having between 1 and 5 carbon atoms;

R₃is iodine, or an alkyl group having between 1 and 5 carbon atoms; and

R₄is hydrogen, a sugar, a polyhydroxy compound, a sulfonic acid salt compound, a carboxylic acid salt compound, or a polyether compound; wherein at least one of R₁, R₂, and R₃comprises iodine.

23. The colorant stabilizing composition of claim 22, wherein the sugar comprises glucose, fructose, a polyether sugar, a monosaccharide, a polysaccharide, or a cyclodextrin.

24. The colorant stabilizing composition of claim 23, wherein the cyclodextrin comprises α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin, sulfated β cyclodextrin and sulfated γ-cyclodextrin.

25. The colorant stabilizing composition of claim 22, wherein R₁, R₂and R₃comprise iodine.

26. The colorant stabilizing composition of claim 22, wherein the colorant stabilizer has one of the following formula:

27. The colorant stabilizing composition of claim 22, wherein the colorant stabilizer has the following formulae:

wherein n is an integer from 1 to 21 and CD represents a cyclodextrin.

28. The colorant stabilizing composition of claim 22, further comprising a molecular includant.

29. The colorant stabilizing composition of claim 22, further comprising a colorant.

30. An ink comprising the colorant stabilizing composition of claim 29.

31. A substrate having thereon the colorant stabilizing composition of claim 22.

32. A colorant stabilizing composition comprising a colorant and a stabilizing molecule represented by the formula

wherein:

R₁is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

R₂is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

R₃is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

R₄is hydrogen, an alkyl, alkenyl, cycloakyl, heterocycloalkyl, aryl, heteroaryl, or substituted aryl group;

R₅is an aryl, heteroaryl, polyalkene, or substituted aryl group; and

wherein R₁, R₂, or R₄are an aryl, heteroaryl, or substituted aryl group.

33. The colorant stabilizing composition of claim 32, wherein the molecule has the formula

wherein

if R₄is an aryl group, then R₂is a hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and

if R₂is an aryl group, then R₄is hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and

R₅is an aryl, heteroaryl, or substituted aryl group.

34. The colorant stabilizing composition of claim 32, wherein the molecule has the following formula

35. The colorant stabilizing composition of claim 32, wherein the molecule has the following formula

36. The colorant stabilizing composition of claim 32, wherein the molecule has the following formula

37. The colorant stabilizing composition of claim 32, wherein the molecule has the following formula

38. The colorant stabilizing composition of claim 32, wherein the molecule has the following formula

39. The colorant stabilizing composition of claim 32, wherein the composition further comprises a molecular includant.

40. The colorant stabilizing composition of claim 39, wherein the molecular includant is covalently bonded to at least one of the stabilizing molecule and the colorant.

41. The colorant stabilizing composition of claim 39, wherein the molecular includant is ethyl hydroxyl β-cyclodextrin.

42. The colorant stabilizing composition of claim 32, further comprising an iodophenol.

43. The colorant stabilizing composition of claim 42, wherein the iodophenol is triiodophenol.

44. The colorant stabilizing composition of claim 32, further comprising a Group VII ion.

45. The colorant stabilizing composition of claim 44, wherein the Group VII ion is iodide.

46. The colorant stabilizing composition of claim 45, wherein iodide is sodium iodide or tetramethyl ammonium iodide.

47. A method of light-stabilizing a colorant comprising associating the colorant with a stabilizing composition, wherein the stabilizing composition comprises a stabilizing molecule represented by the formula

wherein:

R₁is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

R₂is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

R₃is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl group, or substituted aryl group;

R₄is hydrogen, an alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or substituted aryl group;

R₅is an aryl, heteroaryl, polyalkene, or substituted aryl group; and

wherein R₁, R₂, or R₄are an aryl, heteroaryl, or substituted aryl group.

48. The method of claim 47, wherein the molecule has the formula

wherein

if R₄is an aryl group, then R₂is a hydrogen; heterocyclic; alkyl; aryl; or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and

if R₂is an aryl group, then R₄is hydrogen; heterocyclic; alkyl; aryl, or a phenyl group, the phenyl group optionally being substituted with an alkyl, halo, amino, or a thiol group; and

R₅is an aryl, heteroaryl, or substituted aryl group.

49. The method of claim 47, wherein the molecule has the following formula

50. The method of claim 47, wherein the molecule has the following formula

51. The method of claim 47, wherein the molecule has the following formula

52. The method of claim 47, wherein the molecule has the following formula

53. The method of claim 47, wherein the molecule has the following formula

54. The method of claim 47, wherein the composition further comprises a molecular includant.

55. The method of claim 54, wherein the molecular includant is covalently bonded to at least one of the stabilizing molecule and the colorant.

56. The method of claim 54, wherein the molecular includant is ethyl hydroxy β-cyclodextrin.

57. The method of claim 47, wherein the composition further comprises an iodophenol.

58. The method of claim 57, wherein the iodophenol is triiodophenol.

59. The method of claim 47, wherein the composition further comprises a Group VII ion.

60. The method of claim 59, wherein the Group VII ion is iodide.

61. The method of claim 60, wherein the iodide is sodium iodide or tetramethyl ammonium iodide.

62. A colorant stabilizing composition comprising a colorant and a colorant stabilizing agent, wherein the colorant stabilizing agent is a Group VII ion.

63. The composition of claim 62, wherein the Group VII ion is iodide.

64. The composition of claim 63, wherein the iodide is sodium iodide or tetramethyl ammonium iodide.

65. The composition of claim 62, further comprising a molecular includant.

66. The composition of claim 65, wherein the molecular includant is ethyl hydroxy β-cyclodextrin.

67. A method of light stabilizing a colorant comprising associating the colorant with a colorant stabilizing agent, wherein the colorant stabilizing agent is a Group VII ion.

68. The method of claim 67, wherein the Group VII ion is iodide.

69. The method of claim 68, wherein the iodide is sodium iodide or tetramethyl ammonium iodide.

70. The method of claim 67, wherein a molecular includant is associated with the colorant stabilizing agent and the colorant.

71. The method of claim 70, wherein the molecular includant is ethyl hydroxy β-cyclodextrin.

72. A colorant stabilizing composition comprising a colorant and a colorant stabilizing agent, wherein the colorant stabilizing agent is amino sulfonic acid represented by the following formula:

wherein the -SO₃H group is in an ortho, meta or para position relative to the -NH₂group.

73. The composition of claim 72, wherein the colorant stabilizing agent is

74. The method of light stabilizing a colorant comprising associating the colorant with the colorant stabilizing agent of claim 72.

75. A substrate having thereon the colorant stabilizing composition of claim 32.

76. A substrate having thereon the colorant stabilizing composition of claim 62.

77. A substrate having thereon the colorant stabilizing composition of claim 72.

Patent Citations (832)

Patent	Date	Inventor	Cited By
US28225	1974-11-01	Heseltine et al.	Applicant
US28789	1860-04-01	Chang	Applicant
US575228	1997-01-01	von Gallois	Applicant
US582853	1997-05-01	Feer	Applicant
US893636	1908-07-01	Maywald	Applicant
US1013544	1912-01-01	Fuerth	Applicant
US1325971	1919-12-01	Akashi	Applicant
US1364406	1921-01-01	Olsen	Applicant
US1436856	1922-11-01	Brenizer et al.	Applicant
US1744149	1930-01-01	Staehlin	Applicant
US1803906	1931-05-01	Krieger et al.	Applicant
US1844199	1932-02-01	Bicknell et al.	Applicant
US1876880	1932-09-01	Drapal	Applicant
US1880572	1932-10-01	Wendt et al.	Applicant
US1880573	1932-10-01	Wendt et al.	Applicant
US1916350	1933-07-01	Wendt et al.	Applicant
US1916779	1933-07-01	Wendt et al.	Applicant
US1955898	1934-04-01	Wendt et al.	Applicant
US1962111	1934-06-01	Bamberger	Applicant
US2005378	1935-06-01	Kiel	Applicant
US2005511	1935-06-01	Stoll et al.	Applicant
US2049005	1936-07-01	Gaspar	Applicant
US2054390	1936-09-01	Rust et al.	Applicant
US2058489	1936-10-01	Murch et al.	Applicant
US2062304	1936-12-01	Gaspar	Applicant
US2090511	1937-08-01	Crossley et al.	Applicant
US2097119	1937-10-01	Eggert	Applicant
US2106539	1938-01-01	Schnitzspahn	Applicant
US2111692	1938-03-01	Saunders et al.	Applicant
US2125015	1938-07-01	Gaspar	Applicant
US2130572	1938-09-01	Wendt	Applicant
US2132154	1938-10-01	Gaspar	Applicant
US2145960	1939-02-01	Wheatley et al.	Applicant
US2154996	1939-04-01	Rawling	Applicant
US2159280	1939-05-01	Mannes et al.	Applicant
US2171976	1939-09-01	Erickson	Applicant
US2181800	1939-11-01	Crossley et al.	Applicant
US2185153	1939-12-01	Lecher et al.	Applicant
US2220178	1940-11-01	Schneider	Applicant
US2230590	1941-02-01	Eggert et al.	Applicant
US2237885	1941-04-01	Markush et al.	Applicant
US2243630	1941-05-01	Houk et al.	Applicant
US2268324	1941-12-01	Polgar	Applicant
US2281895	1942-05-01	van Poser et al.	Applicant
US2328166	1943-08-01	Poigar et al.	Applicant
US2346090	1944-04-01	Staehle	Applicant
US2349090	1944-05-01	Haddock	Applicant
US2356618	1944-08-01	Rossander et al.	Applicant
US2361301	1944-10-01	Libby, Jr. et al.	Applicant
US2364359	1944-12-01	Kienle et al.	Applicant
US2381145	1945-08-01	von Glahn et al.	Applicant
US2382904	1945-08-01	Federsen	Applicant
US2386646	1945-10-01	Adams et al.	Applicant
US2402106	1946-06-01	von Glahn et al.	Applicant
US2416145	1947-02-01	Biro	Applicant
US2477165	1949-07-01	Bergstrom	Applicant
US2527347	1950-10-01	Bergstrom	Applicant
US2580461	1952-01-01	Pearl	Applicant
US2601669	1952-06-01	Tullsen	Applicant
US2612494	1952-09-01	von Glahn et al.	Applicant
US2612495	1952-09-01	von Glahn et al.	Applicant
US2628959	1953-02-01	von Glahn et al.	Applicant
US2647080	1953-07-01	Joyce	Applicant
US2680685	1954-06-01	Ratchford	Applicant
US2728784	1955-12-01	Tholstrup et al.	Applicant
US2732301	1956-01-01	Robertson et al.	Applicant
US2744103	1956-05-01	Koch	Applicant
US2757090	1956-07-01	Meugebauer et al.	Applicant
US2763550	1956-09-01	Lovick	Applicant
US2768171	1956-10-01	Clarke et al.	Applicant
US2773056	1956-12-01	Helfaer	Applicant
US2798000	1957-07-01	Monterman	Applicant
US2809189	1957-10-01	Stanley et al.	Applicant
US2827358	1958-03-01	Kaplan et al.	Applicant
US2834773	1958-05-01	Scalera et al.	Applicant
US2875045	1959-02-01	Lurie	Applicant
US2892865	1959-06-01	Giraldi et al.	Applicant
US2897187	1959-07-01	Koch	Applicant
US2936241	1960-05-01	Sharp et al.	Applicant
US2940853	1960-06-01	Sagura et al.	Applicant
US2955067	1960-10-01	McBurney et al.	Applicant
US2992129	1961-07-01	Gauthier	Applicant
US2992198	1961-07-01	Funahashi	Applicant
US3030208	1962-04-01	Schellenberg et al.	Applicant
US3071815	1963-01-01	MacKinnon	Applicant
US3075014	1963-01-01	Palopoli et al.	Applicant
US3076813	1963-02-01	Sharp	Applicant
US3104973	1963-09-01	Sprague et al.	Applicant
US3114634	1963-12-01	Brown et al.	Applicant
US3121632	1964-02-01	Sprague et al.	Applicant
US3123647	1964-03-01	Duennenberger et al.	Applicant
US3133049	1964-05-01	Hertel et al.	Applicant
US3140949	1964-07-01	Sprague et al.	Applicant
US3154416	1964-10-01	Fidelman	Applicant
US3155509	1964-11-01	Roscow	Applicant
US3175905	1965-03-01	Wiesbaden	Applicant
US3178285	1965-04-01	Anderau et al.	Applicant
US3238163	1966-03-01	O'Neill	Applicant
US3242215	1966-03-01	Heitmiller	Applicant
US3248337	1966-04-01	Zirker et al.	Applicant
US3266973	1966-08-01	Crowley	Applicant
US3282886	1966-11-01	Gadecki	Applicant
US3284205	1966-11-01	Sprague et al.	Applicant
US3300314	1967-01-01	Rauner et al.	Applicant
US3304297	1967-02-01	Wegmann et al.	Applicant
US3305361	1967-02-01	Gaynor et al.	Applicant
US3313797	1967-04-01	Kissa	Applicant
US3330659	1967-07-01	Wainer	Applicant
US3341492	1967-09-01	Champ et al.	Applicant
US3359109	1967-12-01	Harder et al.	Applicant
US3361827	1968-01-01	Biletch	Applicant
US3363969	1968-01-01	Brooks	Applicant
US3385700	1968-05-01	Willems et al.	Applicant
US3397984	1968-08-01	Williams et al.	Applicant
US3415875	1968-12-01	Luethi et al.	Applicant
US3418118	1968-12-01	Thommes et al.	Applicant
US3445234	1969-05-01	Cescon et al.	Applicant
US3453258	1969-07-01	Parmerter et al.	Applicant
US3453259	1969-07-01	Parmerter et al.	Applicant
US3464841	1969-09-01	Skofronick	Applicant
US3479185	1969-11-01	Chambers	Applicant
US3502476	1970-03-01	Kohei et al.	Applicant
US3503744	1970-03-01	Itano et al.	Applicant
US3514597	1970-05-01	Haes et al.	Applicant
US3541142	1970-11-01	Cragoe, Jr.	Applicant
US3546161	1970-12-01	Wolheim	Applicant
US3547646	1970-12-01	Hori et al.	Applicant
US3549367	1970-12-01	Chang et al.	Applicant
US3553710	1971-01-01	Lloyd et al.	Applicant
US3563931	1971-02-01	Horiguchi	Applicant
US3565753	1971-02-01	Yurkowitz	Applicant
US3574624	1971-04-01	Reynolds et al.	Applicant
US3579533	1971-05-01	Yalman	Applicant
US3595655	1971-07-01	Robinson et al.	Applicant
US3595657	1971-07-01	Robinson et al.	Applicant
US3595658	1971-07-01	Gerlach et al.	Applicant
US3595659	1971-07-01	Gerlach et al.	Applicant
US3607639	1971-09-01	Krefeld et al.	Applicant
US3607693	1971-09-01	Heine et al.	Applicant
US3607863	1971-09-01	Dosch	Applicant
US3615562	1971-10-01	Harrison et al.	Applicant
US3617288	1971-11-01	Hartman et al.	Applicant
US3617335	1971-11-01	Kumura et al.	Applicant
US3619238	1971-11-01	Kimura et al.	Applicant
US3619239	1971-11-01	Osada et al.	Applicant
US3637337	1972-01-01	Pilling	Applicant
US3637581	1972-01-01	Horioguchi et al.	Applicant
US3642472	1972-02-01	Mayo	Applicant
US3647467	1972-03-01	Grubb	Applicant
US3652275	1972-03-01	Baum et al.	Applicant
US3660542	1972-05-01	Adachi et al.	Applicant
US3667954	1972-06-01	Itano et al.	Applicant
US3668188	1972-06-01	King et al.	Applicant
US3669925	1972-06-01	King et al.	Applicant
US3671096	1972-06-01	Mackin	Applicant
US3671251	1972-06-01	Houle et al.	Applicant
US3676690	1972-07-01	McMillin et al.	Applicant
US3678044	1972-07-01	Adams	Applicant
US3689565	1972-09-01	Hoffmann et al.	Applicant
US3694241	1972-09-01	Guthrie et al.	Applicant
US3695879	1972-10-01	Laming et al.	Applicant
US3697280	1972-10-01	Strilko	Applicant
US3705043	1972-12-01	Zablak	Applicant
US3707371	1972-12-01	Files	Applicant
US3729313	1973-04-01	Smith	Applicant
US3737628	1973-06-01	Azure	Applicant
US3765896	1973-10-01	Fox	Applicant
US3775130	1973-11-01	Enomoto et al.	Applicant
US3788849	1974-01-01	Taguchi et al.	Applicant
US3799773	1974-03-01	Watarai et al.	Applicant
US3800439	1974-04-01	Sokolski et al.	Applicant
US3801329	1974-04-01	Sandner et al.	Applicant
US3817752	1974-06-01	Laridon et al.	Applicant
US3840338	1974-10-01	Zviak et al.	Applicant
US3844790	1974-10-01	Chang et al.	Applicant
US3870524	1975-03-01	Watanabe et al.	Applicant
US3873500	1975-03-01	Kato et al.	Applicant
US3876496	1975-04-01	Lozano	Applicant
US3887450	1975-06-01	Gilano et al.	Applicant
US3895949	1975-07-01	Akamatsu	Applicant
US3901779	1975-08-01	Mani	Applicant
US3910993	1975-10-01	Avar et al.	Applicant
US3914165	1975-10-01	Gaske	Applicant
US3914166	1975-10-01	Rudolph et al.	Applicant
US3915824	1975-10-01	McGinniss	Applicant
US3919323	1975-11-01	Houlihan et al.	Applicant
US3926641	1975-12-01	Rosen	Applicant
US3928264	1975-12-01	Young, Jr. et al.	Applicant
US3933682	1976-01-01	Bean	Applicant
US3952129	1976-04-01	Matsukawa et al.	Applicant
US3960685	1976-06-01	Sano et al.	Applicant
US3965157	1976-06-01	Harrison	Applicant
US3978132	1976-08-01	Houlihan et al.	Applicant
US3984248	1976-10-01	Sturmer	Applicant
US3988154	1976-10-01	Sturmer	Applicant
US4004998	1977-01-01	Rosen	Applicant
US4012256	1977-03-01	Levinos	Applicant
US4017652	1977-04-01	Gruber	Applicant
US4022674	1977-05-01	Rosen	Applicant
US4024324	1977-05-01	Sparks	Applicant
US4039332	1977-08-01	Kokelenberg et al.	Applicant
US4043819	1977-08-01	Baumann	Applicant
US4048034	1977-09-01	Martan	Applicant
US4054719	1977-10-01	Cordes, III	Applicant
US4056665	1977-11-01	Tayler et al.	Applicant
US4058400	1977-11-01	Crivello	Applicant
US4067892	1978-01-01	Thorne et al.	Applicant
US4071424	1978-01-01	Dart et al.	Applicant
US4073968	1978-02-01	Miyamoto et al.	Applicant
US4077769	1978-03-01	Garcia	Applicant
US4079183	1978-03-01	Green	Applicant
US4085062	1978-04-01	Virgilio et al.	Applicant
US4090877	1978-05-01	Streeper	Applicant
US4100047	1978-07-01	McCarty	Applicant
US4105572	1978-08-01	Gorondy	Applicant
US4107733	1978-08-01	Schickedanz	Applicant
US4110112	1978-08-01	Roman et al.	Applicant
US4111699	1978-09-01	Krueger	Applicant
US4114028	1978-09-01	Baio et al.	Applicant
US4126412	1978-11-01	Masson et al.	Applicant
US4141807	1979-02-01	Via	Applicant
US4144156	1979-03-01	Kuesters et al.	Applicant
US4148658	1979-04-01	Kondoh et al.	Applicant
US4162162	1979-07-01	Dueber	Applicant
US4171977	1979-10-01	Hasegawa et al.	Applicant
US4179577	1979-12-01	Green	Applicant
US4181807	1980-01-01	Green	Applicant
US4190671	1980-02-01	Vanstone et al.	Applicant
US4199420	1980-04-01	Photis	Applicant
US4229172	1980-10-01	Baumann et al.	Applicant
US4232106	1980-11-01	Iwasaki et al.	Applicant
US4238492	1980-12-01	Majoie	Applicant
US4239843	1980-12-01	Hara et al.	Applicant
US4239850	1980-12-01	Kita et al.	Applicant
US4241155	1980-12-01	Hara et al.	Applicant
US4242430	1980-12-01	Hara et al.	Applicant
US4242431	1980-12-01	Hara et al.	Applicant
US4245018	1981-01-01	Hara et al.	Applicant
US4245995	1981-01-01	Hugl et al.	Applicant
US4246330	1981-01-01	Hara et al.	Applicant
US4248949	1981-02-01	Hara et al.	Applicant
US4250096	1981-02-01	Kvita et al.	Applicant
US4251622	1981-02-01	Kimoto et al.	Applicant
US4254195	1981-03-01	Hara et al.	Applicant
US4256493	1981-03-01	Yokoyama et al.	Applicant
US4256817	1981-03-01	Hara et al.	Applicant
US4258123	1981-03-01	Nagashima et al.	Applicant
US4258367	1981-03-01	Mansukhani	Applicant
US4259432	1981-03-01	Kondoh et al.	Applicant
US4262936	1981-04-01	Miyamoto	Applicant
US4268605	1981-05-01	Hara et al.	Applicant
US4268667	1981-05-01	Anderson	Applicant
US4269926	1981-05-01	Hara et al.	Applicant
US4270130	1981-05-01	Houle et al.	Applicant
US4271252	1981-06-01	Hara et al.	Applicant
US4271253	1981-06-01	Hara et al.	Applicant
US4272244	1981-06-01	Schlick	Applicant
US4276211	1981-06-01	Singer et al.	Applicant
US4277497	1981-07-01	Fromantin	Applicant
US4279653	1981-07-01	Makishima et al.	Applicant
US4279982	1981-07-01	Iwasaki et al.	Applicant
US4279985	1981-07-01	Nonogaki et al.	Applicant
US4284485	1981-08-01	Berner	Applicant
US4288631	1981-09-01	Ching	Applicant
US4289844	1981-09-01	Specht et al.	Applicant
US4290870	1981-09-01	Kondoh et al.	Applicant
US4293458	1981-10-01	Gruenberger et al.	Applicant
US4298679	1981-11-01	Shinozaki et al.	Applicant
US4300123	1981-11-01	McMillin et al.	Applicant
US4301223	1981-11-01	Nakamura et al.	Applicant
US4302606	1981-11-01	Barabas et al.	Applicant
US4306014	1981-12-01	Kunikane et al.	Applicant
US4307182	1981-12-01	Dalzell et al.	Applicant
US4308400	1981-12-01	Felder et al.	Applicant
US4315807	1982-02-01	Felder et al.	Applicant
US4318705	1982-03-01	Nowak et al.	Applicant
US4318791	1982-03-01	Felder et al.	Applicant
US4321118	1982-03-01	Felder et al.	Applicant
US4335054	1982-06-01	Blaser et al.	Applicant
US4335055	1982-06-01	Blaser et al.	Applicant
US4336323	1982-06-01	Winslow	Applicant
US4343891	1982-08-01	Aasen et al.	Applicant
US4345011	1982-08-01	Drexhage	Applicant
US4347111	1982-08-01	Gehlhaus et al.	Applicant
US4349617	1982-09-01	Kawashiri et al.	Applicant
US4350753	1982-09-01	Shelnut et al.	Applicant
US4351893	1982-09-01	Anderson	Applicant
US4356255	1982-10-01	Tachikawa et al.	Applicant
US4357468	1982-11-01	Szejtli et al.	Applicant
US4359524	1982-11-01	Masuda et al.	Applicant
US4362806	1982-12-01	Whitmore	Applicant
US4367072	1983-01-01	Vogtle et al.	Applicant
US4367280	1983-01-01	Kondo et al.	Applicant
US4369283	1983-01-01	Altschuler	Applicant
US4370401	1983-01-01	Winslow et al.	Applicant
US4372582	1983-02-01	Geisler	Applicant
US4373017	1983-02-01	Masukawa et al.	Applicant
US4373020	1983-02-01	Winslow	Applicant
US4374984	1983-02-01	Eichler et al.	Applicant
US4376887	1983-03-01	Greenaway et al.	Applicant
US4383835	1983-05-01	Preuss et al.	Applicant
US4390616	1983-06-01	Sato et al.	Applicant
US4391867	1983-07-01	Derick et al.	Applicant
US4399209	1983-08-01	Sanders et al.	Applicant
US4400173	1983-08-01	Beavan	Applicant
US4401470	1983-08-01	Bridger	Applicant
US4416961	1983-11-01	Drexhage	Applicant
US4421559	1983-12-01	Owatari	Applicant
US4424325	1984-01-01	Tsunoda et al.	Applicant
US4425162	1984-01-01	Sugiyama	Applicant
US4425424	1984-01-01	Altland et al.	Applicant
US4426153	1984-01-01	Libby et al.	Applicant
US4434035	1984-02-01	Eichler et al.	Applicant
US4447521	1984-05-01	Tiers et al.	Applicant
US4450227	1984-05-01	Holmes et al.	Applicant
US4460676	1984-07-01	Fabel	Applicant
US4467112	1984-08-01	Matsuura et al.	Applicant
US4475999	1984-10-01	Via	Applicant
US4477681	1984-10-01	Gehlhaus et al.	Applicant
US4489334	1984-12-01	Owatari	Applicant
US4495041	1985-01-01	Goldstein	Applicant
US4496447	1985-01-01	Eichler et al.	Applicant
US4500355	1985-02-01	Shimada et al.	Applicant
US4508570	1985-04-01	Fugii et al.	Applicant
US4510392	1985-04-01	Litt et al.	Applicant
US4523924	1985-06-01	Lacroix	Applicant
US4524122	1985-06-01	Weber et al.	Applicant
US4534838	1985-08-01	Lin et al.	Applicant
US4548896	1985-10-01	Sabongi et al.	Applicant
US4555474	1985-11-01	Kawamura	Applicant
US4557730	1985-12-01	Bennett et al.	Applicant
US4565769	1986-01-01	Dueber et al.	Applicant
US4567171	1986-01-01	Mangum	Applicant
US4571377	1986-02-01	McGinniss et al.	Applicant
US4595745	1986-06-01	Nakano et al.	Applicant
US4604344	1986-08-01	Irving et al.	Applicant
US4605442	1986-08-01	Kawashita et al.	Applicant
US4613334	1986-09-01	Thomas et al.	Applicant
US4614723	1986-09-01	Schmidt et al.	Applicant
US4617380	1986-10-01	Hinson et al.	Applicant
US4620875	1986-11-01	Shimada et al.	Applicant
US4620876	1986-11-01	Fugii et al.	Applicant
US4622286	1986-11-01	Sheets	Applicant
US4631085	1986-12-01	Kawanishi et al.	Applicant
US4632891	1986-12-01	Banks et al.	Applicant
US4632895	1986-12-01	Patel et al.	Applicant
US4634644	1987-01-01	Irving et al.	Applicant
US4638340	1987-01-01	Iiyama et al.	Applicant
US4647310	1987-03-01	Shimada et al.	Applicant
US4655783	1987-04-01	Reinert et al.	Applicant
US4663275	1987-05-01	West et al.	Applicant
US4663641	1987-05-01	Iiyama et al.	Applicant
US4668533	1987-05-01	Miller	Applicant
US4672041	1987-06-01	Jain	Applicant
US4698291	1987-10-01	Koibuchi et al.	Applicant
US4701402	1987-10-01	Patel et al.	Applicant
US4702996	1987-10-01	Griffing et al.	Applicant
US4704133	1987-11-01	Reinert et al.	Applicant
US4707161	1987-11-01	Thomas et al.	Applicant
US4707425	1987-11-01	Sasagawa et al.	Applicant
US4707430	1987-11-01	Ozawa et al.	Applicant
US4711668	1987-12-01	Shimada et al.	Applicant
US4711802	1987-12-01	Tannenbaum	Applicant
US4713113	1987-12-01	Shimada et al.	Applicant
US4720450	1988-01-01	Ellis	Applicant
US4721531	1988-01-01	Wildeman et al.	Applicant
US4721734	1988-01-01	Gehlhaus et al.	Applicant
US4724021	1988-02-01	Martin et al.	Applicant
US4724201	1988-02-01	Okazaki et al.	Applicant
US4725527	1988-02-01	Robillard	Applicant
US4727824	1988-03-01	Ducharme et al.	Applicant
US4732615	1988-03-01	Kawashita et al.	Applicant
US4737190	1988-04-01	Shimada et al.	Applicant
US4737438	1988-04-01	Ito et al.	Applicant
US4740451	1988-04-01	Kohara	Applicant
US4745042	1988-05-01	Sasago et al.	Applicant
US4746735	1988-05-01	Kruper, Jr. et al.	Applicant
US4752341	1988-06-01	Rock	Applicant
US4755450	1988-07-01	Sanders et al.	Applicant
US4761181	1988-08-01	Suzuki	Applicant
US4766050	1988-08-01	Jerry	Applicant
US4766055	1988-08-01	Kawabata et al.	Applicant
US4770667	1988-09-01	Evans et al.	Applicant
US4772291	1988-09-01	Shibanai et al.	Applicant
US4772541	1988-09-01	Gottschalk	Applicant
US4775386	1988-10-01	Reinert et al.	Applicant
US4786586	1988-11-01	Lee et al.	Applicant
US4789382	1988-12-01	Neumann et al.	Applicant
US4790565	1988-12-01	Steed	Applicant
US4797080	1980-04-01	Mee	Applicant
US4800149	1989-01-01	Gottschalk	Applicant
US4803008	1989-02-01	Ciolino et al.	Applicant
US4808189	1989-02-01	Oishi et al.	Applicant
US4812139	1989-03-01	Brodmann	Applicant
US4812517	1989-03-01	West	Applicant
US4813970	1989-03-01	Kirjanov et al.	Applicant
US4822714	1989-04-01	Sanders	Applicant
US4831068	1989-05-01	Reinert et al.	Applicant
US4834771	1989-05-01	Yamauchi et al.	Applicant
US4837106	1989-06-01	Ishikawa et al.	Applicant
US4837331	1989-06-01	Yamanishi et al.	Applicant
US4838938	1989-06-01	Tomida et al.	Applicant
US4839269	1989-06-01	Okazaki et al.	Applicant
US4849320	1989-07-01	Irving et al.	Applicant
US4853037	1989-08-01	Johnson et al.	Applicant
US4853398	1989-08-01	Carr et al.	Applicant
US4854971	1989-08-01	Gane et al.	Applicant
US4857438	1989-08-01	Loerzer et al.	Applicant
US4861916	1989-08-01	Kohler et al.	Applicant
US4865942	1989-09-01	Gottschalk et al.	Applicant
US4874391	1989-10-01	Reinert	Applicant
US4874899	1989-10-01	Hoelderich et al.	Applicant
US4885395	1989-12-01	Hoelderich	Applicant
US4886774	1989-12-01	Doi	Applicant
US4892941	1990-01-01	Dolphen et al.	Applicant
US4895880	1990-01-01	Gottschalk	Applicant
US4900581	1990-02-01	Stuke et al.	Applicant
US4902299	1990-02-01	Anton	Applicant
US4902725	1990-02-01	Moore	Applicant
US4902787	1990-02-01	Freeman	Applicant
US4911732	1990-03-01	Neumann et al.	Applicant
US4911899	1990-03-01	Hagiwara et al.	Applicant
US4917956	1990-04-01	Rohrbach	Applicant
US4921317	1990-05-01	Suzuki et al.	Applicant
US4925770	1990-05-01	Ichiura et al.	Applicant
US4925777	1990-05-01	Inoue et al.	Applicant
US4926190	1990-05-01	Lavar	Applicant
US4933265	1990-06-01	Inoue et al.	Applicant
US4933948	1990-06-01	Herkstroeter	Applicant
US4937161	1990-06-01	Kita et al.	Applicant
US4942113	1990-07-01	Trundle	Applicant
US4950304	1990-08-01	Reinert et al.	Applicant
US4952478	1990-08-01	Miyagawa et al.	Applicant
US4952680	1990-08-01	Schmeidl	Applicant
US4954380	1990-09-01	Kanome et al.	Applicant
US4954416	1990-09-01	Wright et al.	Applicant
US4956254	1990-09-01	Washizu et al.	Applicant
US4964871	1990-10-01	Reinert et al.	Applicant
US4965294	1990-10-01	Ohngemach et al.	Applicant
US4966607	1990-10-01	Shinoki et al.	Applicant
US4966833	1990-10-01	Inoue	Applicant
US4968596	1990-11-01	Inoue et al.	Applicant
US4968813	1990-11-01	Rule et al.	Applicant
US4985345	1991-01-01	Hayakawa et al.	Applicant
US4987056	1991-01-01	Imahashi et al.	Applicant
US4988561	1991-01-01	Wason	Applicant
US4997745	1991-03-01	Kawamura et al.	Applicant
US5001330	1991-03-01	Koch	Applicant
US5002853	1991-03-01	Aoai et al.	Applicant
US5002993	1991-03-01	West et al.	Applicant
US5003142	1991-03-01	Fuller	Applicant
US5006758	1991-04-01	Gellert et al.	Applicant
US5013959	1991-05-01	Kogelschatz	Applicant
US5017195	1991-05-01	Satou et al.	Applicant
US5023129	1991-06-01	Morganti	Applicant
US5025036	1991-06-01	Carson et al.	Applicant
US5026425	1991-06-01	Hindagolla et al.	Applicant
US5026427	1991-06-01	Mitchell et al.	Applicant
US5028262	1991-07-01	Barlow, Jr. et al.	Applicant
US5028792	1991-07-01	Mullis	Applicant
US5030243	1991-07-01	Reinert	Applicant
US5030248	1991-07-01	Meszaros	Applicant
US5034526	1991-07-01	Bonham et al.	Applicant
US5037726	1991-08-01	Kojima et al.	Applicant
US5045435	1991-09-01	Adams et al.	Applicant
US5045573	1991-09-01	Kohler et al.	Applicant
US5047556	1991-09-01	Kohler et al.	Applicant
US5049777	1991-09-01	Mechtersheimer	Applicant
US5053320	1991-10-01	Robbillard	Applicant
US5055579	1991-10-01	Pawlowski et al.	Applicant
US5057562	1991-10-01	Reinert	Applicant
US5068364	1991-11-01	Takagaki et al.	Applicant
US5069681	1991-12-01	Bouwknegt et al.	Applicant
US5070001	1991-12-01	Stahlhofen	Applicant
US5073448	1991-12-01	Vieira et al.	Examiner
US5074885	1991-12-01	Reinert	Applicant
US5076808	1991-12-01	Hahn et al.	Applicant
US5085698	1992-02-01	Ma et al.	Applicant
US5087550	1992-02-01	Blum et al.	Applicant
US5089050	1992-02-01	Vieira et al.	Examiner
US5089374	1992-02-01	Saeva	Applicant
US5096456	1992-03-01	Reinert et al.	Applicant
US5096489	1992-03-01	Laver	Applicant
US5096781	1992-03-01	Vieira et al.	Applicant
US5098477	1992-03-01	Vieira et al.	Examiner
US5098793	1992-03-01	Rohrbach et al.	Applicant
US5098806	1992-03-01	Robillard	Applicant
US5106723	1992-04-01	West et al.	Applicant
US5108505	1992-04-01	Moffat	Applicant
US5108874	1992-04-01	Griffing et al.	Applicant
US5110706	1992-05-01	Yumoto et al.	Applicant
US5110709	1992-05-01	Aoai et al.	Applicant
US5114832	1992-05-01	Zertani et al.	Applicant
US5124723	1992-06-01	Laver	Applicant
US5130227	1992-07-01	Wade et al.	Applicant
US5133803	1992-07-01	Moffatt	Applicant
US5135940	1992-08-01	Belander et al.	Applicant
US5139572	1992-08-01	Kawashima	Applicant
US5139687	1992-08-01	Borgher, Sr. et al.	Applicant
US5141556	1992-08-01	Matrick	Applicant
US5141797	1992-08-01	Wheeler	Applicant
US5144964	1992-09-01	Demian	Applicant
US5147901	1992-09-01	Rutsch et al.	Applicant
US5153104	1992-10-01	Rossman et al.	Applicant
US5153105	1992-10-01	Sher et al.	Applicant
US5153166	1992-10-01	Jain et al.	Applicant
US5160346	1992-11-01	Fuso et al.	Applicant
US5160372	1992-11-01	Matrick	Applicant
US5166041	1992-11-01	Murofushi et al.	Applicant
US5169436	1992-12-01	Matrick	Applicant
US5169438	1992-12-01	Matrick	Applicant
US5173112	1992-12-01	Matrick et al.	Applicant
US5176984	1993-01-01	Hipps Sr. et al.	Applicant
US5178420	1993-01-01	Shelby	Applicant
US5180425	1993-01-01	Matrick et al.	Applicant
US5180652	1993-01-01	Yamaguchi et al.	Applicant
US5181935	1993-01-01	Reinert et al.	Applicant
US5185236	1993-02-01	Shiba et al.	Applicant
US5187045	1993-02-01	Bonham et al.	Applicant
US5187049	1993-02-01	Sher et al.	Applicant
US5190565	1993-03-01	Berenbaum et al.	Applicant
US5190710	1993-03-01	Kletecka	Applicant
US5190845	1993-03-01	Hashimoto et al.	Applicant
US5193854	1993-03-01	Borowski, Jr. et al.	Applicant
US5196295	1993-03-01	Davis	Applicant
US5197991	1993-03-01	Rembold	Applicant
US5198330	1993-03-01	Martic et al.	Applicant
US5202209	1993-04-01	Winnik, et al.	Applicant
US5202210	1993-04-01	Matsuoka, et al.	Applicant
US5202211	1993-04-01	Vercoulen	Applicant
US5202212	1993-04-01	Shin, et al.	Applicant
US5202213	1993-04-01	Nakahara, et al.	Applicant
US5202215	1993-04-01	Kanakura et al.	Applicant
US5202221	1993-04-01	Imai et al.	Applicant
US5205861	1993-04-01	Matrick	Applicant
US5208136	1993-05-01	Zanoni et al.	Applicant
US5209814	1993-05-01	Felten et al.	Applicant
US5219703	1993-06-01	Bugner et al.	Applicant
US5221334	1993-06-01	Ma et al.	Applicant
US5224197	1993-06-01	Zanoni et al.	Applicant
US5224476	1993-07-01	Schultz et al.	Applicant
US5224987	1993-07-01	Matrick	Applicant
US5226957	1993-07-01	Wickramanayake et al.	Applicant
US5227022	1993-07-01	Leonhardt et al.	Applicant
US5241059	1993-08-01	Yoshinaga	Applicant
US5244476	1993-09-01	Schultz et al.	Applicant
US5250109	1993-10-01	Chan et al.	Applicant
US5254429	1993-10-01	Gracia et al.	Applicant
US5256193	1993-10-01	Winnik et al.	Applicant
US5258274	1993-11-01	Helland et al.	Applicant
US5261953	1993-11-01	Vieira et al.	Examiner
US5262276	1993-11-01	Kawamura	Applicant
US5268027	1993-12-01	Chan et al.	Applicant
US5270078	1993-12-01	Walker et al.	Applicant
US5271764	1993-12-01	Winnik et al.	Applicant
US5271765	1993-12-01	Ma	Applicant
US5272201	1993-12-01	Ma et al.	Applicant
US5275646	1994-01-01	Marshall et al.	Applicant
US5279652	1994-01-01	Kaufmann et al.	Applicant
US5282894	1994-02-01	Albert et al.	Applicant
US5284734	1994-02-01	Blum et al.	Applicant
US5286286	1994-02-01	Winnik et al.	Applicant
US5286288	1994-02-01	Tobias et al.	Applicant
US5294528	1994-03-01	Furutachi	Applicant
US5296275	1994-03-01	Goman et al.	Applicant
US5296556	1994-03-01	Frihart	Applicant
US5298030	1994-03-01	Burdeska et al.	Applicant
US5300403	1994-04-01	Angelopolus et al.	Applicant
US5300654	1994-04-01	Nakajima et al.	Applicant
US5302195	1994-04-01	Helbrecht	Applicant
US5302197	1994-04-01	Wickramanayke et al.	Applicant
US5310778	1994-05-01	Shor et al.	Applicant
US5312713	1994-05-01	Yokoyama et al.	Applicant
US5312721	1994-05-01	Gesign	Applicant
US5324349	1994-06-01	Sano et al.	Applicant
US5328504	1994-07-01	Ohnishi	Applicant
US5330860	1994-07-01	Grot et al.	Applicant
US5334455	1994-08-01	Noren et al.	Applicant
US5338319	1994-08-01	Kaschig et al.	Applicant
US5340631	1994-08-01	Matsuzawa et al.	Applicant
US5340854	1994-08-01	Martic et al.	Applicant
US5344483	1994-09-01	Hinton	Applicant
US5356464	1994-10-01	Hickman et al.	Applicant
US5362592	1994-11-01	Murofushi et al.	Applicant
US5368689	1994-11-01	Agnemo	Applicant
US5372387	1994-12-01	Wajda	Applicant
US5372917	1994-12-01	Tsuchida et al.	Applicant
US5374335	1994-12-01	Lindgren et al.	Applicant
US5376503	1994-12-01	Audett et al.	Applicant
US5383961	1995-01-01	Bauer et al.	Applicant
US5384186	1995-01-01	Trinh	Applicant
US5393580	1995-02-01	Ma et al.	Applicant
US5401303	1995-03-01	Stoffel et al.	Applicant
US5401562	1995-03-01	Akao	Applicant
US5415686	1995-05-01	Kurabayashi et al.	Applicant
US5415976	1995-05-01	Ali	Applicant
US5424407	1995-06-01	Tanaka et al.	Applicant
US5425978	1995-06-01	Berneth et al.	Applicant
US5426164	1995-06-01	Babb et al.	Applicant
US5427415	1995-06-01	Chang	Applicant
US5429628	1995-07-01	Trinh et al.	Applicant
US5431720	1995-07-01	Nagai et al.	Applicant
US5432274	1995-07-01	Luong et al.	Applicant
US5445651	1995-08-01	Thoen et al.	Applicant
US5445842	1995-08-01	Tanaka et al.	Applicant
US5455143	1995-10-01	Ali	Applicant
US5459014	1995-10-01	Nishijima et al.	Applicant
US5464472	1995-11-01	Horn et al.	Applicant
US5466283	1995-11-01	Kondo et al.	Applicant
US5474691	1995-12-01	Severns	Applicant
US5475080	1995-12-01	Gruber et al.	Applicant
US5476540	1995-12-01	Shields et al.	Applicant
US5479949	1996-01-01	Battard et al.	Applicant
US5489503	1996-02-01	Toan	Applicant
US5498345	1996-03-01	Jollenbeck et al.	Applicant
US5501774	1996-03-01	Burke	Applicant
US5503664	1996-04-01	Sano et al.	Applicant
US5509957	1996-04-01	Toan et al.	Applicant
US5531821	1996-07-01	Wu	Applicant
US5532112	1996-07-01	Kohler et al.	Applicant
US5541633	1996-07-01	Winnike et al.	Applicant
US5543459	1996-08-01	Hartmann et al.	Applicant
US5571313	1996-11-01	Mafune et al.	Applicant
US5575891	1996-11-01	Trokhan et al.	Applicant
US5580369	1996-12-01	Belding et al.	Applicant
US5607803	1997-03-01	Murofushi et al.	Applicant
US5782963	1998-07-01	Nohr et al.	Examiner
US5855655	1999-01-01	Nohr et al.	Examiner
US5885337	1999-03-01	Nohr et al.	Examiner
AU103085	1937-04-01		Applicant
AU12624/88	1988-09-01		Applicant
BE620075	1962-05-01		Applicant
BE637169	1964-03-01		Applicant
CA413257	1932-10-01		Applicant
CA458808	1936-12-01		Applicant
CA460268	1949-10-01		Applicant
CA461082	1949-11-01		Applicant
CA463021	1950-02-01		Applicant
CA463022	1950-02-01		Applicant
CA465496	1950-05-01		Applicant
CA465495	1950-05-01		Applicant
CA465499	1950-05-01		Applicant
CA483214	1952-05-01		Applicant
CA517364	1955-10-01		Applicant
CA537687	1957-03-01		Applicant
CA552565	1958-02-01		Applicant
CA571792	1959-03-01		Applicant
CA779239	1968-02-01		Applicant
CA930103	1973-07-01		Applicant
CA2053094	1992-04-01		Applicant
CH603767	1978-08-01		Applicant
CH197808	1988-05-01		Applicant
CZ94118	1958-05-01		Applicant
DE1047787	1957-12-01		Applicant
DE1022801	1958-01-01		Applicant
DE1039835	1958-09-01		Applicant
DE1040562	1958-10-01		Applicant
DE1045414	1958-12-01		Applicant
DE1047013	1958-12-01		Applicant
DE1132540	1962-07-01		Applicant
DE1154069	1963-09-01		Applicant
DE1240811	1967-05-01		Applicant
DE2202497	1972-08-01		Applicant
DE2432563	1975-02-01		Applicant
DE2437380	1975-02-01		Applicant
DE2444520	1975-03-01		Applicant
DE2416259	1975-10-01		Applicant
DE2714978	1977-10-01		Applicant
DE2722264	1978-11-01		Applicant
DE3126433	1983-01-01		Applicant
DE158237	1983-01-01		Applicant
DE3415033	1984-10-01		Applicant
DE271512	1989-09-01		Applicant
DE3921600	1990-01-01		Applicant
DE3833437	1990-04-01		Applicant
DE3833438	1990-04-01		Applicant
DE4036328	1991-07-01		Applicant
DE4132288	1992-04-01		Applicant
DE4126461	1993-02-01		Applicant
EP3884	1979-09-01		Applicant
EP29284	1981-05-01		Applicant
EP127574	1984-12-01		Applicant
EP223587	1987-05-01		Applicant
EP262533	1988-04-01		Applicant
EP280458	1988-08-01		Applicant
EP308274	1989-03-01		Applicant
EP351615	1990-01-01		Applicant
EP375160	1990-06-01		Applicant
EP373662	1990-06-01		Applicant
EP371304	1990-06-01		Applicant
EP390439	1990-10-01		Applicant
EP458140A1	1991-10-01		Applicant
EP458140	1991-11-01		Applicant
EP468465	1992-01-01		Applicant
EP542286	1993-05-01		Applicant
EP571190	1993-11-01		Applicant
EP608433	1994-08-01		Applicant
EP609159	1994-08-01		Applicant
EP639664	1995-02-01		Applicant
FR2245010	1975-04-01		Applicant
FR2383157	1978-10-01		Applicant
GB275245	1928-10-01		Applicant
GB349339	1931-05-01		Applicant
GB355686	1931-08-01		Applicant
GB399753	1933-10-01		Applicant
GB441085	1936-01-01		Applicant
GB463515	1937-04-01		Applicant
GB492711	1938-09-01		Applicant
GB518612	1940-03-01		Applicant
GB539912	1941-09-01		Applicant
GB626727	1947-07-01		Applicant
GB600451	1948-04-01		Applicant
GB616362	1949-01-01		Applicant
GB618616	1949-02-01		Applicant
GB779389	1957-07-01		Applicant
GB1372884	1974-11-01		Applicant
GB2146357	1985-04-01		Applicant
GB1772118	1992-10-01		Applicant
IT662500	1964-04-01		Applicant
JP424756			Applicant
JP43-15663	1968-07-01		Applicant
JP47-26653	1972-07-01		Applicant
JP47-45409	1972-11-01		Applicant
JP49-8909	1974-02-01		Applicant
JP50-65592	1975-06-01		Applicant
JP51-17802	1976-02-01		Applicant
JP53-104321	1978-09-01		Applicant
JP55-62059	1980-05-01		Applicant
JP55-90506	1980-07-01		Applicant
JP56-14569	1981-02-01		Applicant
JP56-0014233	1981-02-01		Applicant
JP56-24472	1981-03-01		Applicant
JP56-36556	1981-04-01		Applicant
JP57-61055	1982-04-01		Applicant
JP57-128283	1982-08-01		Applicant
JP57-171775	1982-10-01		Applicant
JP58-1244452	1983-07-01		Applicant
JP58-125770	1983-07-01		Applicant
JP58-222164	1983-12-01		Applicant
JP59-89360	1984-05-01		Applicant
JP59-29219270	1984-12-01		Applicant
JP59-219270	1985-04-01		Applicant
JP60-192729	1985-10-01		Applicant
JP60-239741	1985-11-01		Applicant
JP60-239739	1985-11-01		Applicant
JP60-239740	1985-11-01		Applicant
JP60-239743	1985-11-01		Applicant
JP61-3781	1986-01-01		Applicant
JP61-288	1986-01-01		Applicant
JP61-14995	1986-01-01		Applicant
JP61-21184	1986-01-01		Applicant
JP61-14994	1986-01-01		Applicant
JP61-40366	1986-02-01		Applicant
JP61-30592	1986-02-01		Applicant
JP61-25885	1986-02-01		Applicant
JP61-128973	1986-06-01		Applicant
JP61-97025	1986-09-01		Applicant
JP61-222789	1986-10-01		Applicant
JP61-247703	1986-11-01		Applicant
JP61-285403	1986-12-01		Applicant
JP62-7703	1987-01-01		Applicant
JP62-100557	1987-05-01		Applicant
JP62-97881	1987-05-01		Applicant
JP62-127281	1987-06-01		Applicant
JP63-43959	1988-02-01		Applicant
JP63-48370	1988-03-01		Applicant
JP63-95446	1988-04-01		Applicant
JP63-95447	1988-04-01		Applicant
JP63-95449	1988-04-01		Applicant
JP63-95440	1988-04-01		Applicant
JP63-95445	1988-04-01		Applicant
JP63-95439	1988-04-01		Applicant
JP63-95450	1988-04-01		Applicant
JP63-95448	1988-04-01		Applicant
JP63-151946	1988-06-01		Applicant
JP63-165498	1988-07-01		Applicant
JP63-164953	1988-07-01		Applicant
JP63-223078	1988-09-01		Applicant
JP63-223077	1988-09-01		Applicant
JP63-243101	1988-10-01		Applicant
JP63-199781	1988-12-01		Applicant
JP64-29337	1989-01-01		Applicant
JP64-15049	1989-01-01		Applicant
JP64-40948	1989-02-01		Applicant
JP64-89014948	1989-03-01		Applicant
JP1-128063	1989-05-01		Applicant
JP1-146974	1989-06-01		Applicant
JP1-210477	1989-08-01		Applicant
JP1-288854	1989-11-01		Applicant
JP2-58573	1990-02-01		Applicant
JP2-92957	1990-04-01		Applicant
JP2-179642	1990-07-01		Applicant
JP2-282261	1990-11-01		Applicant
JP3-134072	1991-06-01		Applicant
JP3-170415	1991-07-01		Applicant
JP3-163566	1991-07-01		Applicant
JP3-206439	1991-09-01		Applicant
JP3-284668	1991-12-01		Applicant
JP3-203694	1991-12-01		Applicant
JP4-023884	1992-01-01		Applicant
JP4-023885	1992-01-01		Applicant
JP4-45174	1992-02-01		Applicant
JP4-100801	1992-04-01		Applicant
JP4-136075	1992-05-01		Applicant
JP4-356087	1992-12-01		Applicant
JP5-43806	1993-02-01		Applicant
JP5-61220	1993-03-01		Applicant
JP5-080506	1993-04-01		Applicant
JP5-134447	1993-05-01		Applicant
JP5-119506	1993-05-01		Applicant
JP5-140498	1993-06-01		Applicant
JP2-219869	1993-09-01		Applicant
JP5-263067	1993-10-01		Applicant
JP6-80915	1994-03-01		Applicant
JP6-116555	1994-04-01		Applicant
JP6-116556	1994-04-01		Applicant
JP6-116557	1994-04-01		Applicant
JP6-175584	1994-06-01		Applicant
JP6-214339	1994-08-01		Applicant
JP6-256633	1994-09-01		Applicant
JP6-256494	1999-09-01		Applicant
NL7113828	1972-04-01		Applicant
RU1310767	1987-05-01		Applicant
WO92/11295	1992-07-01		Applicant
WO93/06597	1993-04-01		Applicant
WO94/01503	1994-01-01		Applicant
WO94/22501	1994-10-01		Applicant
WO94/22500	1994-10-01		Applicant
WO95/04955	1995-02-01		Applicant
WO96/00740	1996-01-01		Applicant
WO96/19502	1996-06-01		Applicant
WO96/22335	1996-07-01		Applicant

Non-Patent Literature (222)

Kubat et al. “Photophysical properties of metal complexes of meso-tetrakis (40sulphonatophenyl) porphyrin,” J. Photochem. and Photobiol. 96 93-97 1996, no month available.Applicant
Abstract for WO 95/00343-A1 Textiles: Paper: Cellulose p. 7 1995, no month available.Applicant
Maki, Y. et al. “A novel heterocyclic N-oxide, pyrimido[5,4-g]pteridinetetrone 5-oxide, with multifunctional photooxidative properties” Chemical Abstracts 122 925 [no 122:31350F] 1995, no month available.Applicant
Abstract of patent, JP 6-80915 (Canon Inc.), Mar. 22, 1994.Applicant
Abstract of patent, JP 06-43573 (Iku Meji) (Feb. 18, 1994).Applicant
Pitchumani, K. “Modification of chemical reactivity upon cyclodextrin encapsulation” Chemical Abstracts 121 982 [no. 121:133624v] 1994, no month available.Applicant
Derwent Publications Ltd., London, JP 05297627 (Fujitsu Ltd.), Nov. 12, 1993. (Abstract).Applicant
Patent Abstracts of Japan, JP 5241369 (Bando Chem Ind Ltd et al.), Sep. 21, 1993. (Abstract).Applicant
Derwent Publications Ltd., London, JP 05232738 (Yamazaki, T.), Sep. 10, 1993. (Abstract).Applicant
Derwent Publications Ltd., London, EP 000559310 (Zeneca Ltd.), Sep. 8, 1993. (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 5-230410 (Seiko Epson Corp), Sep. 7, 1993. (Abstract).Applicant
Derwent Publications Ltd., London, JP 5-230407 (Mitsubishi Kasei Corp), Sep. 7, 1993. (Abstract).Applicant
Abstract Of Patent, JP 405230410 (Seiko Epson Corp.), Sep. 7, 1993. (Abstract).Applicant
Abstract Of Patent, JP 405230407 ( Mitsubishi Kasei Corp.), Sep. 7, 1993. (Abstract).Applicant
Patent Abstracts of Japan, JP 5197198 (Bando Chem Ind Ltd et al.), Aug. 6, 1993. (Abstract).Applicant
Database WPI -Derwent Publications Ltd., London, J,A, 5197069 (Bando Chem), Aug. 6, 1993. (Abstract).Applicant
Abstract of patent, JP 5-195450 (Nitto Boseki Co. Ltd), Aug. 3, 1993.Applicant
Patent Abstracts of Japan, JP 5181308 (Bando Chem Ind Ltd et al.), Jul. 23, 1993. (Abstract).Applicant
Patent Abstracts of Japan, JP 5181310 (Bando Chem Ind Ltd et al.), Jul. 23, 1993. (Abstract).Applicant
Derwent Publications Ltd., London, JP 5-132638 (Mitsubishi Kasei Corp), May 28, 1993 (Abstract).Applicant
Abstract Of Patent, JP 405132638 (Mitsubishi Kasei Corp.), May 28, 1993. (Abstract)Applicant
Derwent Publications Ltd., London JP 5-125318 (Mitsubishi Kasei Corp), May 21,1993. ( Abstract).Applicant
Abstract Of Patent, JP 405125318 (Mitsubishi Kasei Corp.), May 21, 1993. (Abstract).Applicant
Abstract of patent, JP 05-117200 (Hidefumi Hirai et al.) (May 14, 1993).Applicant
Derwent World Patents Index, JP 5117105 (Mitsui Toatsu Chem Inc.) May 14, 1993.Applicant
Derwent Publications Ltd., London JP 05061246 (Ricoh KK), Mar. 12, 1993. (Abstract).Applicant
Husain, N. et al. “Cyclodextrins as mobile-phase additives in reversed-phase HPLC” American Laboratory 82 80-87 1993, no month available.Applicant
Hamilton, D.P. “Tired of Shredding? New Ricoh Method Tries Different Tack” Wall Street Journal B2 1993, no month available.Applicant
“Cyclodextrins: A Breakthrough for Molecular Encapsulation” American Maize Products Co. (Amaizo) 1993, no month available.Applicant
Duxbury “The Photochemistry and Photophysics of Triphenylmethane Dyes in Solid Liquid Media” Chemical Review 93 381-433 1993, no month available.Applicant
Abstract of patent, JP 04-351603 (Dec. 7, 1992).Applicant
Abstract of patent, JP 04-351602 1992, no month available.Applicant
Derwent Publications Ltd., London, JP 40314796 (Citizen Watch Co. Ltd.), Nov. 5, 1992. (Abstract).Applicant
Abstract of patent, JP 04315739 1992, no month available.Applicant
Derwent Publications Ltd., London, JP 04300395 (Funai Denki KK), Oct. 23, 1992. (Abstract).Applicant
Derwent Publications Ltd., London, JP 404213374 (Mitsubishi Kasei Corp), Aug. 4, 1992. (Abstract).Applicant
Abstract of patent, JP 04-210228 1992, no month available.Applicant
Abstract Of Patent, JP 404202571 (Canon Inc.), Jul. 23, 1992. (Abstract).Applicant
Abstract Of Patent, JP 404202271 (Mitsubishi Kasei Corp.), Jul. 23, 1992. (Abstract).Applicant
Derwent Publications Ltd., London, JP 4-189877 (Seiko Epson Corp), Jul. 8, 1992. (Abstract).Applicant
Derwent Publications Ltd., London JP 404189876 (Seiko Epson Corp), Jul. 8, 1992. (Abstract).Applicant
Abstract Of Patent, JP 404189877 (Seiko Epson Corp.), Jul. 8, 1992. (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 4-170479 (Seiko Epson Corp), Jun. 18, 1992. (Abstract).Applicant
Abstract of patent, JP 04-81402 1992, no month available.Applicant
Abstract of patent, JP 04-81401 1992, no month available.Applicant
Kogelschatz “Silent-discharge driven excimer UV sources and their applications” Applied Surface Science 410-423 1992, no month available.Applicant
Derwent Publications, Ltd., London, JP 403269167 (Japan Wool Textile KK), Nov. 29, 1991 (Abstract).Applicant
Derwent Publications Ltd., London, JO 3247676 (Canon KK), Nov. 5, 1991 (Abstract).Applicant
Abstract of patent, JP 03-220384 1991, no month available.Applicant
Patent Abstracts of Japan, JP 03184896 (Dainippon Printing Co Ltd.) Aug. 12, 1991.Applicant
Derwent Publications Ltd., London, JP 3167270 (Mitsubishi Kasei Corp), Jul. 19, 1991. (Abstract).Applicant
Derwent Publications Ltd., London, JO 3167270 (Mitsubishi Kasei Corp.), Jul. 19, 1991 (Abstract).Applicant
Derwent Publications Ltd., London, JO 3093870 (Dainippon Ink Chem KK.), Apr. 18, 1991 (Abstract).Applicant
Abstract of patent, JP 06369890 1991, no month available.Applicant
Kogelschatz, U. et al. “New Excimer UV Sources for Industrial Applications” ABB Review 391 1-10 1991, no month available.Applicant
Abstract of patent, JP 03-41165 1991, no month available.Applicant
“Coloring/Decoloring Agent for Tonor Use Developed” Japan Chemical Week 1991, no month available.Applicant
Braithwaite, M., et al. “Formulation” Chemistry & Technology UV & EB Formulation for Coatings, Inks & Paints IV 11-12 1991, no month available.Applicant
Scientific Polymer Products, Inc. Brochure 24-31 1991, no month available.Applicant
Dietliker, K. “Photoiniators for Free Radical and Catioinc Polymerisation” Chem & Tech of UV & EB Formulation for Coatings, Inks & Paints III 61,63, 229-232, 280, 405, 1991, no month available.Applicant
Esrom et al. “Large area Photochemical Dry Etching of Polymers iwth incoherent Excimer UV Radiation” MRS Materials Research Society 1-7 1991, no month available.Applicant
Esrom et al. Excimer Laser-Induced Decomposition of Aluminum Nitride Materials Research Society Fall Meeting 1-6 1991, no month available.Applicant
Esrom et al. “Metal deposition with a windowless VUV excimer source” Applied Surface Science 1-5 1991, no month available.Applicant
Esrom “Excimer Laser-Induced Surface Activation of Aln for Electroless Metal Deposition” Mat. Res. Sco.1Symp. Proc. 204 457-465 1991, no month available.Applicant
Zhang et al. “UV-induced decompositin of adsorbed Cu-acetylacetonate films at room temperature for electroless metal plating” Applied Surface Science 1-6, no month availble.Applicant
“German company develops reuseable paper” Pulp & Paper 1991, no monh available.Applicant
Abstract of patent, JP 02289652 1990, no month available.Applicant
Ohashi et al. “Molecular Mechanics Studies on inclusion Compounds of Cyanine Dye Monomers and Dimers in Cyclodextrin Cavities,” J. Am. Chem. Soc. 112 5824-5830 1990, no month available.Applicant
Kogelschatz et al. “new Incoherent Ultraviolet Excimer Sources for Photolytic Material Deposition,”Laser Und Optoelektronik 1990, no month available.Applicant
Patent Abstracts of Japan, JP 02141287 (Dainippon Printing Co Ltd.) May 30, 1990.Applicant
Abstract of Patent, JP 0297957, (Fuji Xerox Co., Ltd.) 1990, no month available.Applicant
Derwent Publications Ltd., London, JP 2091166 (Canon KK), Mar 30, 1990. (abstract).Applicant
Esrom et al. “Metal Deposition with Incoherent Excimer Radiation” Mat. Res. Soc. Proc. 158 189-198 1990, no month available.Applicant
Esrom “UV Excimer Laser-Induced Deposition of Palladium from palladiym Acetate Films” Mat. Res. Soc. Symp. Proc. 158 109-117 1990, no month available.Applicant
Kogelschatz U. “Silent Discharges for the Generation of ultraviolet and vacuum ultraviolet excimer radiation” Pure & Applied Chem. 62 1667-74 1990, no month available.Applicant
Esrom et al. “Investigation of the mechanism of the UV-induced palladium depostions process from thin sold palladium acetate films” Applied Surface Science 46 158-162 1990, no month available.Applicant
Zhang et al. “VUV synchrontron radiation processing of thin palladium acetate spin-on films for metallic surface patterning” Applied Surface Science 46 153-157 1990, no month available.Applicant
Brennan et al. “Stereoelectronic effects in ring closure reactions: the 2'-hydroxychalcone -Flavanone equilibrium, and related systems,” Canadian J. Chem. 68 pp. 1780-(10) 1785 1990, no month available.Applicant
Abstract of patent, JP 01-299083 1989, no month available.Applicant
Derwent Publications Ltd., London, J,O, 1182379 (Canon KK), Jul. 20, 1989. (Abstract) 1989.Applicant
Derwent Publications Ltd., London, JO 10111171 (Mitsubishi Chem Ind. KK.), Jan. 13, 1989 (Abstract) 1989.Applicant
Gruber, R. J., et al. “Xerographic Materials” Encyclopedia of Polymer Science and Engineering 17 918-943 1989, no month available.Applicant
Pappas, S. P. “Photocrosslinking” Comph. Pol. Sci. 6 135-148 1989, no month available.Applicant
Pappas, S. P. “Photoinitiated Polymerization” Comph. Pol. Sci. 4 337-355 1989, no month available.Applicant
Kirilenko, G. V. et al. “An analog of the vesicular process with amplitude modulation of the incident light beam” Chemical Abstracts 111 569 [no. 111:12363 3b] 1989, no month available.Applicant
Esrom et al. “UV excimer laser-induced pre-nucleation of surfaces followed by electroless metallization” Chemtronics 4 216-223 1989, no month available.Applicant
Esrom et al. “VUV light-induced depostion of palladium using an incoherent Xe2* excimer source” Chemtronics 4 1989, no month Available.Applicant
Esrom et al. “UV Light-Induced Deposition of Copper Films” C5-719-C5-725 1989, no month available.Applicant
Falbe et al. Rompp Chemie Lexikon 9 270 1989, no month available.Applicant
Derwent Publications, Ltd., London, SU 1423656 (Kherson Ind Inst), Sep. 15, 1988 (Abstract) 1988.Applicant
Derwent Publications, Ltd., London, EP 0280653 (Ciba GeigyAG), Aug. 31, 1988 (Abstract).Applicant
Abstract of patent, JP 63-190815 1988, no month available.Applicant
Patent Abstracts of Japan, JP 63179985 (Tomoegawa Paper Co. Ltd.), Jul. 23, 1988.Applicant
Derwent World Patents Index, JP 63179977 (Tomoegawa Paper Mfg Co Ltd), Jul. 23, 1988.Applicant
Furcone, S. Y. et al. “Spin-on B14Sr3Ca3Cu4O16+x superconducting thin films from citrate precursors,” Appl. Phys. Lett. 52(2 2180-2182 5) 1988, no month available.Applicant
Abstract of patent, JP 63-144329 1988, no month available.Applicant
Abstract of patent, JP 63-130164 1988, no month available.Applicant
Derwent Publications, Ltd., London, J6 3112770 (Toray Ind Inc), May 17, 1988 (Abstract).Applicant
Derwent Publications, Ltd. London, J6 3108074 (Konishiroku Photo KK), May 12, 1988 (Abstract).Applicant
Derwent Publications, Ltd., London,J6 3108073 (Konishiroku Photo KK), May 12, 1988 (Abstract).Applicant
Abstract of patent, JP 61-77846 1988, no month available.Applicant
Abstract of patent, JP 63-73241 1988, no month available.Applicant
Abstract of patent, JP 63-47762, 1988, no month available.Applicant
Abstract of patent, JP 63-47763, 1988, no month available.Applicant
Abstract of patent, JP 63-47764, 1988 no month available.Applicant
Abstract of patent, JP 63-47765 1988, no month available.Applicant
Eliasson, B., et al. “UV Excimer Radiation from Dielectric-Barrier Discharges” Applied Physics B 46 299-303 1988, no month available.Applicant
Eliasson et al. “New Trends in High Intensity UV Generation” EPA Newsletter (32 29-40 1988, no month available.Applicant
Cotton, F. A. “Oxygen: Group Via(16)” Advanced Inorganic Chemistry 5th 473-474 ed. 1988, no mont available.Applicant
Derwent Publications, Ltd., London, J6 2270665 (Konishiroku Photo KK), Nov. 25, 1987 (Abstract).Applicant
Abstract of patent, JP 62-215261 1987, no month available.Applicant
Database WPI, Derwent Publications Ltd., London, JP 62032082 (Mitsubishi Denki KK), Feb. 12, 1987. (Abstract).Applicant
Abstract of patent, JP 62-32082 1987, no month available.Applicant
Derwent Publications Ltd., London, J6 2007772 (ALPS Electric KK.), Jan. 14, 1987 (Abstract).Applicant
Gross et al. “Laser direct-write metallization in thin palladium acetate films” J. App. Phys. 61 1628-1632 (4) 1987, no month available.Applicant
Al-Ismail et al. “Some experimental results on thin polypropylene films loaded with finely-dispersed copper” Journal of Materials Science 415-418 1987, no month available.Applicant
Baufay et al. “Optical self-regulation during laser-induced oxidation of copper” J. Appl. Phys 61 4640-4651 (9) 1987, no month available.Applicant
Derwent Publications Ltd., London, JA 0284478 (Sanyo Chem Ind Ltd.), Dec. 15, 1986 (Abstract).Applicant
Abstract of patent, JP 61251842 1986, no month available.Applicant
Database WPI, Derwent Publications Ltd., London, GB; SU, A, 1098210 (Kutulya L A) Jun. 23, 1986.Applicant
Abstract of patent, JP 61-97025 1986, no month available.Applicant
Abstract of patent, JP 61-87760 1986, no month available.Applicant
Derwent Publications Ltd., London, DL 0234731 (Karl Marx Univ. Leipzig), May 9, 1986. (Abstract).Applicant
Derwent World Patents Index, SU 1219612 (AS USSR NON-AQ SOLN) Mar. 23, 1986.Applicant
Derwent Publications, Ltd. London, J6 1041381 (Osaka Prefecture), Feb. 27, 1986. (Abstract).Applicant
Dialog, JAPIO, JP 61-034057 (Ciba Geig AG) Feb. 18, 1986.Applicant
Derwent World Patents Index, JP 61027288 (sumitomo Chem Ind KK) Feb. 6, 1986.Applicant
Sakai et al. “A Novel and Practical Synthetic Method of 3(2H)-Furanone Derivatives,” J. Heterocyclie Chem. 23 pp. 1199-1201 1989, no month available.Applicant
Jellinek, H. H. G. et al. “Evolution of H2O and CO2 During the Copper-Catalyzed Oxidation of Isotactic Polypropylene,” J. Polymer Sci. 24 389-403 1986, no month available.Applicant
Jellinek, H. H. G. et al. “Diffusion of Ca2+ Catalysts from Cu-Metal Polymer or Cu-Oxide/Polymer Interfaces into Isotactic Polypropylene,” J. Polymer Sci. 24 503-510 1986, no month available.Applicant
John J. Eisch and Ramiro Sanchez “Selective, Oxophilic Imination of Ketones with Bis (dichloraluminum) Phenylimide” J. Org. Chem. 51 1848-1852 (10) 1986, no month available.Applicant
Derwent Publications Ltd., London, J6 0226575 (Sumitomo Chem Ind Ltd.), Oct. 11, 1985 (Abstract).Applicant
Abstract of patent, JP 60-156761 1985, no month available.Applicant
Derwent Publications Ltd., London, J,A, 0011451 (Fugi Photo Film KK), Jan. 21, 1985. (Abstract).Applicant
Derwent Publications, Ltd., London J6 0011449 -A (Taoka Chemical KK) Jan. 21, 1985 (Abstract).Applicant
Roos, G. et al. “Textile applications of photocrosslinkable polymers” Chemical Abstracts 103 57 [no. 103:23690j] 1985, no month available.Applicant
Derwent World Patents Index, EP 127574 (Ciba Geigy AG), Dec. 5, 1984.Applicant
Derwent Publications Ltd., London JP 0198187 (Donon KK), Nov. 9, 1984. (Abstract)Applicant
Derwent Publications Ltd., London, J,A, 0169883 (Ricoh KK), Sep. 25, 1994. (Abstract).Applicant
Derwent Publications Ltd., London, JA 0169883 (Ricoh KK), Sep. 25, 1984 (Abstract).Applicant
Derwent Publications Ltd., London, JA 0198187 (Canon KK), Nov. 9, 1984 (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0053563 (Dainippon Toryo KK), Mar. 28, 1984. (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0053562 (Dainippon Toryo KK), Mar. 28, 1984. (Abstract).Applicant
Abstract of Patent, JA 0053563 (Dainippon Toryo KK), Mar. 28, 1984 (Abstract)Applicant
Abstract of Patent, JA 0053562 (Dainippon Toryo KK), Mar. 28, 1984 (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0051961 (Dainippon Toryo KK), Mar. 26, 1984. (Abstract).Applicant
Abstract of Patent, JA 0051961 (Dainippon Toryo KK), Mar. 26, 1984 (Abstract).Applicant
Saenger, W. “Structural Aspects of Cyclodextrins and Their Inclusion Complexes” Inclusion Compounds -Structural Aspects of Inclusion Compounds formed by Organic Host 2 231-259 1984, no month available.Applicant
Szejtli “Industrial Applications of Cyclodextrins” Inclusion Compounds Physical Prop. & Applns 3 331-390 1984, no month available.Applicant
Kano et al. “Three-Component Complexes of Cyclodextrins. Exciplex Formation in Cyclodextrin Cavity.” J. Inclusion Phenomena 2 pp. 737-746 1984, no month available.Applicant
Suzuki et al. “Spectroscopic Investigation of Cyclodextrin Monomers, Derivatives, Polymers and Azo Dyes.” J. Inclusion Phenomena 2, pp. 715-724 1984, no month available.Applicant
Abstract of Patent, JA 0222164 (Ricoh KK), Dec. 23, 1983 (Abstract).Applicant
Abstract of patent, JP 58211426 (Sekisui Plastics KK), (Dec. 8, 1993).Applicant
Derwent Publications, Ltd., London, EP 0072775 (Ciba Geigy AG), Feb. 23, 1983 (Abstract).Applicant
van Beek, H. C. A “Light-Induced Colour Changes in Dyes and Materials” Color Res. and Appl. 8 176-181 1983, no month available.Applicant
Connors, K. A. “Application of a stoichiometric model of cyclodextrin complex formation” Chemical Abstracts 98 598 [no. 98:53067g] 1983, no month available.Applicant
Abstract of Patent, EP 0065617 (IBM Corp.), Dec. 1, 1982 (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0187289 (Honshu Paper Mfg KK), Nov. 17, 1982. (Abstract).Applicant
Abstract of Patent, JA 0187289 (Honsho Paper Mfg KK), Nov. 17, 1982 (Abstract).Applicant
Abstract of Patent, JA 0185364 (Ricoh KK), Nov. 15, 1982. (Abstract).Applicant
Derwent Publications, Ltd. London J5 7139146 (Showa Kako KK) Aug. 27, 1982 (abstract).Applicant
Abstract of Patent, JA 00900069 (Canon KK), Jun. 4, 1982 (Abstract).Applicant
Derwent Publications, Ltd., London, JA 0061785 (Nippon Senka KK), Apr. 14, 1982 (Abstract).Applicant
Fischer, “Submicroscopic contact imaging with visible light by energy transfer” Appl. Phys. Letter 40(3 1982, no month available.Applicant
Abstract of Patent, JA 0010659 (Canon KK), Jan. 20, 1982 (Abstract).Applicant
Abstract of Patent, JA 0010661 (Canon KK), Jan. 20, 1982 (Abstract).Applicant
Christen “Carbonylverbindungen: Aldehyde und Ketone,” Grundlagen der Organischen Chemie 255 1982, no month available.Applicant
Derwent Publications Ltd., London, J,A, 0155263 (Canon KK), Dec. 1, 1981. (Abstract).Applicant
Abstract of Patent, JA 0155263 (Canon KK), Dec. 1, 1981 (Abstract).Applicant
Abstract of Patent, JA 0147861 (Canon KK), Nov. 17, 1981 (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0143273 (Canon KK), Nov. 7, 1981. (Abstract).Applicant
Abstract of Patent, JP 56143272 (Canon KK), Nov. 7, 1981 (Abstract).Applicant
Abstract of Patent, JA 0136861 (Canon KK), Oct. 26, 1981 (Abstract).Applicant
Abstract of Patent, JA 6133378 (Canon KK), Oct. 19, 1981 (Abstract).Applicant
Abstract of Patent, JA 6133377 (Canon KK), Oct. 19, 1981 (Abstract).Applicant
Abstract of Patent, JA 6093775 (Canon KK), Jul. 29, 1981 (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0008135 (Ricoh KK), Jan. 27, 1981. (Abstract).Applicant
Derwent Publications Ltd., London, J,A, 0004488 (Canon KK), Jan. 17, 1981. (Abstract).Applicant
Abstract of Patent, JA 0004488 (Canon KK), Jan. 17, 1981 (Abstract).Applicant
Kirk-Othmer “Metallic Coatings,” Encyclopedia of Chemical Technology 15 241-274 1981, no month available.Applicant
Komiyama et al. “One-Pot Preparation of 4-Hydroxychalcone β-Cyclodextrin as Catalyst,” Makromol. Chem. 2 733-734 1981, no month available.Applicant
Derwent Publications, Ltd., London CA 1086-719 (Sherwood Medical) Sep. 30, 1980 (abstract).Applicant
Rosanske et al. “Stoichiometric Model of Cyclodextrin Complex Formation” Journal of Pharmaceutical Sciences 69 564-567 (5) 1980, no month available.Applicant
Semple et al. “Synthesis of Functionalized Tetrahydrofurans,” Tetrahedron Letters 81 pp. 4561-4564 1980, no month available.Applicant
Kirk-Othmer “Film Deposition Techniques,” Encyclopedia of Chemical Technology 10 247-283 1980, no month available.Applicant
Derwent World Patents Index, Derwent Info. Ltd., JP 54158941 (Toyo Pulp KK), Dec. 15, 1979. (Abstract).Applicant
Derwent World Patents Index, JP 54117536 (Kawashima F) Sep. 12, 1979.Applicant
Derwent Publications Ltd., London, J,A, 0005422 (Fuji Photo Film KK), Jan. 16, 1979. (Abstract).Applicant
Drexhage et al. “Photo-bleachable dyes and Processes” Research Disclosure 85-87 1979, no month available.Applicant
“Color imaging devices and color filter arrays using photo-bleachable dyes” Research Disclosure 22-23 1979, no month available.Applicant
Wolff, N. E., et al. “Electrophotography” Kirk-Othmer Encyclopedia of Chemical Technology 8 794-826 1979, no month available.Applicant
Derwent Publications Ltd., London, J,A, 0012037 (Pentel KK), Jan. 29, 1977. (Abstract).Applicant
Abstract of Patent, JA 0012037 (Pentel KK), Jan. 29, 1977 (Abstract).Applicant
Jenkins, P. W. et al. “Photobleachable dye material” Research Disclosure 18 [no. 12932] 1975, no month available.Applicant
Lamberts, R. L. “Recording color grid patterns with lenticules” Research Disclosure 18-19 [no. 12923] 1975, no month available.Applicant
Karmanova, L. S. et al. “Light stabilizers of daytime fluorescent paints” Chemical Abstracts 82 147 [no 59971p] 1975, no month available.Applicant
Prokopovich, B. et al. “Selection of effective photoinducers for rapid hardening of polyester varnish PE-250” Chemical Abstracts 83 131 [no 81334a] 1975, no month available.Applicant
“Variable Constrast Printing System” Research Disclosure 19 [no. 12931] 1975, no month available.Applicant
Lakshman “Electronic Absorption Spectrum of Copper Formate Tetrahydrate” Chemical Physics Letters 31 331-334 (2) 1975, no month available.Applicant
Derwent Publications, Ltd., London J4 9131-226 (TNational Cash Register C) Dec. 16, 1974 (abstract).Applicant
Chang, I. F., et al. “Color Modulated Dye Ink Jet Printer” IBM Technical Disclosure Bulletin 17(5 1520-1521, 1974, no month available.Applicant
“Darocur 1173: Liquid Photoiniator for Ultraviolet Curing of Coatings” 1974, no month available.Applicant
Hosokawa et al.“Ascofuranone, an antibiotic from Ascochyta,” Japan Kokai 73 91,278 (Nov. 28, 1973) MERCK Index 80 p. 283; abstract 94259t 1974, no month available.Applicant
Abstract of patent, NL 7112489 (Dec. 27, 1971).Applicant
Gafney et al. “Photochemical Reactions of Copper (II) -1,3-Diketonate Complexes” Journal of the Americqal Chemical Society 1971, no month available.Applicant
Derwent Publications, Ltd., London SU 292698-S Jan. 15, 1971 (abstract).Applicant
Derwent World Patents Index,CS 120380 (Kocourek, Jan) Oct. 15, 1966.Applicant
Rigdon, J. E. “In Search of Paper that Spies Can't Copy” Wall Street Journal, no date available.Applicant
Chatterjee, S. et al. “Photochemistry of Carbocyanine Alkyltriphenylborate Salts: Intra-Ion-Pair Electron Transfer and the Chemistry of Boranyl Radicals” J. Am. Chem. Soc. 112 6329-6338, no date available.Applicant
“Assay -Physical and Chemical Analysis of Complexes” AMAIZO, no date available.Applicant
“Cyclodextrin” AMAIZO, no date available.Applicant
“Beta Cyclodextrin Polymer (BCDP)” AMAIZO, no date available.Applicant
“Chemically Modified Cyclodextrins” AMAIZO, no date available.Applicant
“Cyclodextrin Complexation” American Maize Products Co., no date available.Applicant
“Monomers” Scientific Polymer Products Inc., no date available.Applicant
Suppan, Paul “Quenching of Excited States” Chemistry and Light 65-69, no date available.Applicant
Yamaguchi, H. et al. “Supersensitization. Aromatic ketones as supersensitizers” Chemical Abstracts 53 107 (d), no date available.Applicant
Stecher, H. “Ultraviolet-absorptive additives in adhesives, lacquers and plastics” Chemical Abstracts 53 14579 (c), no date available.Applicant
Maslennikov, A. S. “Coupling of diazonium with ketones” Chemical Abstracts 60 3128e, no date available.Applicant
Derwent Publications Ltd., London 4 9128022, no date available.Applicant
Abstract of Patent, JP 405195450, no date available.Applicant
Rose, Philip I. “Gelatin,” Encyclopedia of Chemical Technology 7 488-513, no date available.Applicant

Colorant stabilizers

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